Polymers containing macromonomers

ABSTRACT

Polymers are disclosed which comprise: 
     (A) about 1-99.9 weight percent of one or more alpha, beta-monoethylenically unsaturated carboxylic acids, typically methacrylic acids; 
     (B) about 0-98.9 weight percent of one or more monoethylenically unsaturated monomers, typically ethyl acrylate; 
     (C) about 0.1-99 weight percent of one or more monoethylenically unsaturated macromonomers, and 
     (D) about 0-20 weight percent or greater of one or more polyethylenically unsaturated monomers. These polymers can be solubilized in water with the aid of an alkali, like ammonium hydroxide. When the polymers are added to latex paints and neutralized, the viscosity of the paint is increased, brush drag is increased, and the paint rheology is otherwise improved.

RELATED APPLICATIONS

This application is a Division of prior U.S. application Ser. No.08/163,487, filed Dec. 7, 1993, now U.S. Pat. No. 5,342,883 and which isa division of application Ser. No. 07/887,647, filed May 29, 1992, nowU.S. Pat. No. 5,292,843.

The following are related, commonly assigned applications, filed on aneven date herewith:

U.S. patent application Ser. No. 07/887,645; U.S. patent applicationSer. No. 07/887,646; U.S. patent application Ser. No. 07/887,642; U.S.patent application Ser. No. 07/887,673; U.S. patent application Ser. No.07/887,672; U.S. patent application Ser. No. 07/887,641 now U.S. Pat.No. 5,292,828; U.S. patent application Ser. No. 07/887,648; U.S. patentapplication Ser. No. 07/887,643; U.S. patent application Ser. No.07/887,644; and U.S. patent application Ser. No. 07/887,671 nowabandoned; all of which are incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION

1. Technical Field

This invention relates to polymers which are soluble in, or swelled by,an aqueous alkaline medium to provide thickeners for use in aqueouscoating compositions, especially latex paints.

2. Background of the Invention

Thickeners for aqueous systems are needed for various purposes, such asfor architectual coatings, industrial coatings, automotive coatings andthe like to improve rheology of the coatings. Hydroxyethyl cellulose isa well known thickener for aqueous systems, but it has variousdeficiencies in that excessive amounts must be used and the theology ofthe thickened system is inadequate. Various ethoxylatedcarboxyl-functional polymers which form alkali soluble thickeners arealso known, but these have various deficiencies, including inadequatehydrolytic stability.

It has long been desired to provide superior thickeners for aqueoussystems which are highly efficient, which better resist hydrolysis, andwhich provide better rheology. This is achieved herein by providing newpolymers which possess these desired characteristics.

DISCLOSURE OF THE INVENTION

This invention relates in part to polymers comprising:

(A) about 1-99.9, preferably about 10-70, weight percent of one or morealpha, beta-monoethylenically unsaturated carboxylic acids, typicallymethacrylic acid;

(B) about 0-98.9, preferably about 30-85, weight percent of one or moremonoethylenically unsaturated monomers, typically ethyl acrylate;

(C) about 0.1-99, preferably about 5-60, weight percent of one or moremonoethylenically unsaturated macromonomers; and

(D) about 0-20, preferably about 0-10, weight percent or greater of oneor more polyethylenically unsaturated monomers, typically trimethylolpropane triacrylate.

This invention also relates in part to an emulsion of theabove-identified polymer in water, which emulsion is useful as athickening agent in aqueous compositions. In order to obtain thethickening effect, the polymer is dissolved in the aqueous compositionto be thickened.

This invention further relates in part to an aqueous composition, andmore particularly an improved latex paint composition containing theabove-defined polymer.

This invention yet further relates in part to a process for thickeningan aqueous composition which comprises adding the above-defined polymerto an aqueous composition and dissolving the polymer in the aqueouscomposition.

DETAILED DESCRIPTION

A large proportion of one or more alpha, beta-monoethylenicallyunsaturated carboxylic acid monomers can be present in the polymers ofthis invention. Various carboxylic acid monomers can be used, such asacrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylicacid, crotonic acid, fumaric acid, citraconic acid, mesaconic acid,itaconic acid, maleic acid and the like including mixtures thereof.Methacrylic acid is preferred. A large proportion of carboxylic acidmonomer is essential to provide a polymeric structure which willsolubilize and provide a thickener when reacted with an alkali likesodium hydroxide.

The polymers of this invention can also contain a significant proportionof one or more monoethylenically unsaturated monomers. The preferredmonomers provide water insoluble polymers when homopolymerized and areillustrated by acrylate and methacrylate esters, such as ethyl acrylate,butyl acrylate or the corresponding methacrylate. Other monomers whichcan be used are styrene, alkyl styrenes, vinyl toluene, vinyl acetate,vinyl alcohol, acrylonitrile, vinylidene chloride, vinyl ketones and thelike. Nonreactive monomers are preferred, those being monomers in whichthe single ethylenic group is the only group reactive under theconditions of polymerization. However, monomers which include groupsreactive under baking conditions or with divalent metal ions such aszinc oxide may be used in some situations, like hydroxyethyl acrylate.

Other illustrative monoethylenically unsaturated monomers useful in thisinvention include, for example, propyl methacrylate, isopropylmethacrylate, butyl methacrylate, n-amyl methacrylate, sec-amylmethacrylate, hexyl methacrylate, lauryl methacrylate, stearylmethacrylate, ethyl hexyl methacrylate, crotyl methacrylate, cinnamylmethacrylate, oleyl methacrylate, ricinoleyl methacrylate, hydroxy ethylmethacrylate, hydroxy propyl methacrylate, vinyl propionate, vinylbutyrate, vinyl tert-butyrate, vinyl caprate, vinyl stearate, vinyllaurate, vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyln-propyl ether, vinyl iso-propyl ether, vinyl n-butyl ether, vinyliso-butyl ether, vinyl iso-octyl ether, vinyl phenyl ether,α-chlorovinyl phenyl ether, vinyl β-naphthyl ether, methacryonitrile,acrylamide, methacrylamide, N-alkyl acrylamides, N-aryl acrylamides,N-vinyl pyrrolidone, N-vinyl-3-morpholinones, N-vinyl-oxazolidone,N-vinyl-imidazole and the like including mixtures thereof.

The macromonomers useful in this invention can be represented by theformula: ##STR1## wherein: R¹ is a monovalent residue of a substitutedor unsubstituted complex hydrophobe compound;

each R² is the same or different and is a substituted or unsubstituteddivalent hydrocarbon residue;

R³ is a substituted or unsubstituted divalent hydrocarbon residue;

R⁴, R⁵ and R⁶ are the same or different and are hydrogen or asubstituted or unsubstituted monovalent hydrocarbon residue; and

z is a value of 0 or greater.

The macromonomer compounds useful in this invention can be prepared by anumber of conventional processes, except for inclusion of the complexhydrophobe compounds described herein. Illustrative processes a redescribed, for example, in U.S. Pat. Nos. 4,514,552, 4,600,761,4,569,965, 4,384,096, 4,268,641, 4,138,381, 3,894,980, 3,896,161,3,652,497, 4,509,949, 4,226,754, 3,915,921, 3,940,351, 3,035,004,4,429,097, 4,421,902, 4,167,502, 4,764,554, 4,616,074, 4,464,524,3,657,175, 4,008,202, 3,190,925, 3,794,608, 4,338,239, 4,939,283 and3,499,876. The macromonomers can also be prepared by methods disclosedin copending U.S. patent application Ser. No. (D-17010), which isincorporated herein by reference.

Illustrative substituted and unsubstituted divalent hydrocarbon residuesrepresented by R² in formula I above include those described for thesame type of substituents in formulae (i) and (ii) below. Illustrativesubstituted and unsubstituted monovalent hydrocarbon residuesrepresented by R⁴, R⁵ and R⁶ in formula I above include those describedfor the same type of substituents in formula (i) and (ii) below.

Illustrative R³ substituents include, for example, the organic residueof ethers, esters, urethanes, amides, ureas, urethanes, anhydrides andthe like including mixtures thereof. The R³ substituent can be generallydescribed as a "linkage" between the complex hydrophobe bearingsurfactant or alcohol, and the unsaturation portion of the macromonomercompound. Preferred linkages include the following: urethane linkagesfrom the reaction of an isocyanate with a nonionic surfactant; urealinkages from the reaction of an isocyanate with an amine bearingsurfactant; unsaturated esters of surfactants such as the esterificationproduct of a surfactant with of an unsaturated carboxylic acid or anunsaturated anhydride; unsaturated esters of alcohols; esters of ethylacrylate oligomers, acrylic acid oligomers, and allyl containingoligomers; half esters of surfactants such as those made by the reactionof a surfactant with maleic anhydride; unsaturated ethers prepared byreacting vinyl benzyl chloride and a surfactant or by reacting an allylglycidyl ether with a surfactant, alcohol, or carboxylic acid.

The oxyalkylene moieties included in the macromonomer compounds (I) maybe homopolymers or block or random copolymers of straight or branchedalkylene oxides. Mixtures of alkylene oxides such as ethylene oxide andpropylene oxide may be employed. It is understood that each R² group ina particular substituent for all positive values of z can be the same ordifferent.

The complex hydrophobe compounds having at least one active hydrogenuseful in preparing the macromonomer compounds useful in this inventioncan be represented by the formula: ##STR2## wherein R₁ and R₂ are thesame or different and are hydrogen or a substituted or unsubstitutedmonovalent hydrocarbon residue, R₃ is a substituted or unsubstituteddivalent or trivalent hydrocarbon residue, each R₄ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, each R₅ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, R₆ is hydrogen, asubstituted or unsubstituted monovalent hydrocarbon residue or an ionicsubstituent, a and b are the same or different and are a value of 0 or1, and x and y are the same or different and are a value of 0 orgreater; provided at least two of R₁, R₂, R₃, R₄, R₅ and R₆ are ahydrocarbon residue having greater than 2 carbon atoms in the case ofR₁, R₂ and R₆ or having greater than 2 pendant carbon atoms in the caseof R₃, R₄ and R₅. For purposes of the polymers and macromonomers offormula (I) above, when z is a value of 0 and R¹ is the residue of acomplex hydrophobe of formula (i) in which R₁ is hexadecyl, a is a valueof 1, R₂ is tetradecyl, b is a value of 0, R₃ is ##STR3## R₄ is --CH₂CH(tetradecyl)--, x is a value of 1, R₅ is --CH₂ CH₂ --, y is a value of34, R₆ is hydrogen, and the --R³ --(R⁴)C═CR⁵ R⁶ portion of themacromonomer is the residue of maleic anhydride, then the polymers ofthis invention are other than a terpolymer of said macromonomer, styreneand maleic anhydride. Also for purposes of the polymers andmacromonomers of formula (I) above, when R² is --CH₂ CH₂ --, z is avalue of 34 and R¹ is the residue of a complex hydrophobe of formula (i)in which R₁ is hexadecyl, a is a value of 1, R₂ is tetradecyl, b is avalue of 0, R₃ is ##STR4## R₄ is --CH₂ CH(tetradecyl)--, x is a value of1, y is a value of 0, R₆ is hydrogen, and the --R³ --(R₄)C═CR⁵ R⁶portion of the macromonomer is the residue of maleic anhydride, then thepolymers of this invention are other than a terpolymer of saidmacromonomer, styrene and maleic anhydride.

Other complex hydrophobe compounds having at least one active hydrogenuseful in preparing the macromonomer compounds useful in this inventioncan be represented by the formula: ##STR5## wherein R₇ and R₈ are thesame or different and are hydrogen or a substituted or unsubstitutedmonovalent hydrocarbon residue, R₁₁ and R₁₄ are the same or differentand are hydrogen, a substituted or unsubstituted monovalent hydrocarbonresidue or an ionic substituent, R₉ and R₁₂ are the same or differentand are a substituted or unsubstituted divalent or trivalent hydrocarbonresidue, each R₁₀ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, each R₁₃ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, R₁₅ is a substituted or unsubstituted divalent hydrocarbonresidue, d and e are the same or different and are a value of 0 or 1,and f and g are the same or different and are a value of 0 or greater;provided at least two of R₇, R₈, R₉, R₁₀, R₁₁ R₁₂, R₁₃, R₁₄ and R₁₅ area hydrocarbon residue having greater than 2 carbon atoms in the case ofR₇, R₈, R₁₁ and R₁₄ or having greater than 2 pendant carbon atoms in thecase of R₉, R₁₀, R₁₂, R₁₃ and R₁₅.

Illustrative substituted and unsubstituted monovalent hydrocarbonresidues contain from 1 to about 50 carbon atoms or greater and areselected from alkyl radicals including linear or branched primary,secondary or tertiary alkyl radicals, such as methyl, ethyl, n-propyl,isopropyl, amyl, sec-amyl, t-amyl, 2-ethylhexyl and the like; arylradicals such as phenyl, naphthyl and the like; arylalkyl radicals suchas benzyl, phenylethyl, tri-phenylmethylethane and the like; alkylarylradicals such as octylphenyl, nonylphenyl, dodecylphenyl, tolyl, xylyland the like; and cycloalkyl radicals such as cyclopentyl, cyclohexyl,cyclohexylethyl and the like. The permissible hydrocarbon residues maycontain fluorine, silicon, or other non-carbon atoms.

Preferably, the substituted and unsubstituted hydrocarbon residues areselected from alkyl and aryl radicals which contain from about 1 to 30carbon atoms or greater. More preferably, the alkyl radicals containfrom 1 to 18 carbon atoms, while the aryl, arylalkyl, alkylaryl andcycloalkyl radicals preferably contain from 6 to 18 carbon atoms orgreater.

In a preferred embodiment of this invention, R₁, R₂, R₇ and R₈ canindividually be a hydrocarbon radical represented by the formula:##STR6## wherein R₁₆ and R₁₇ are as defined for R₁, R₂, R₇ and R₈ above,h and i are the same or different and are a value of 0 or 1, and R₁₈ isas defined for R₃ above. For compounds represented by formulae (i) and(ii), it is understood that each formula (iii) radical in a givencompound may be the same or different and the R₁₆ and/or R₁₇ groups maythemselves be a formula (iii) radical to provide complex hydrophobes ofa dendritic or of a cascading nature as described below. Further, R₄,R₅, R₁₀ and R₁₃ can individually be a hydrocarbon radical represented bythe formula:

    --CH[(OR.sub.19).sub.j OR.sub.20 ]--                       (iv)

wherein R₁₉ is as defined for R₄, R₅, R₁₀ and R₁₃ above, R₂₀ is asdefined for R₆, R₁₁ and R₁₄ above, and j is a value of 0 or greater.

Illustrative ionic substituents for R₆, R₁₁, R₁₄ and R₂₀ includecationic and anionic substituents such as sulfates, sulfonates,phosphates and the like. R₆, R₁₁, R₁₄ and R₂₀ may preferably be anorganic residue containing 1 or more hydroxyls or nitrogen derivativesor epoxides or other reactive groups which may or may not containunsaturation.

Other illustrative terminal groups which are described by R₆, R₁₁, R₁₄and R₂₀ include, for example, hydrocarbon residues which may containallylic or vinylic unsaturation, acrylic or methacrylic functionality,styryl or alpha-methylstyryl functionality, and the like, such as thereaction product between the terminal alcohol (R₆, R₁₁, R₁₄ and R₂₀ =H)and glycidyl methacrylate, isocyanatoethyl methacrylate, alpha,alpha-dimethyl-m-isopropenyl benzyl isocyanate (m-TMI), and the like.Other examples of terminal groups may include hydrocarbon residues ofalkyl, aryl, aralkyl, alkaryl, and cycloalkyl radicals which may or maynot be substituted with one or more of the following: hydroxyl,carboxyl, isocyanato, amino, mono- or disubstituted amino, quaternaryammonium, sulfate, sulfonate, phosphate, epoxy, and the like and may ormay not contain other non-carbon atoms including silicon or fluorine.Also included can be divalent siloxy radicals. Other nonhydrocarbonterminal groups may include sulfates, phosphates, and the like.

Illustrative divalent hydrocarbon residues represented by R₃, R₄, R₅,R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉ in the above formulae includesubstituted and unsubstituted radicals selected from alkylene,-alkylene-oxy-alkylene-, -arylene-oxy-arylene-, arylene, alicyclicradicals, phenylene, naphthylene, -phenylene-(CH₂)_(m) (Q)_(n) (CH₂)_(m)-phenylene- and -naphthylene-(CH₂)_(m) (Q)_(n) (CH₂)_(m) -naphthylene-radicals, wherein Q individually represents a substituted orunsubstituted divalent bridging group selected from --CR₂₁ R₂₂ --,--O--, --S--, --NR₂₃ --, --SiR₂₄ R₂₅ -- and --CO--, wherein R₂₁ and R₂₂individually represent a radical selected from hydrogen, alkyl of 1 to12 carbon atoms, phenyl, tolyl and anisyl; R₂₃, R₂₄ and R₂₅ individuallyrepresent a radical selected from hydrogen and methyl, and each m and nindividually have a value of 0 or 1. More specific illustrative divalentradicals represented by R₃, R.sub. 4, R₅, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈and R₁₉ include, e.g., 1,1-methylene, 1,2-ethylene, 1,3-propylene,1,6-hexylene, 1,8-octylene, 1,12-dodecylene, 1,4-phenylene,1,8-napthylene, 1,1'-biphenyl-2,2'-diyl, 1,1'-binaphthyl-2,2'-diyl,2,2'-binaphthyl-1,1'-diyl and the like. The alkylene radicals maycontain from 2 to 12 carbon atoms or greater, while the arylene radicalsmay contain from 6 to 18 carbon atoms or greater. Preferably, R₃, R₄,R₅, R₉, R₁₀, R₁₂, R₁₃, R₁₅, R₁₈ and R₁₉ are an alkylene or aryleneradical. The permissible divalent hydrocarbon residues may containfluorine, silicon, or other non-carbon atoms.

Illustrative trivalent hydrocarbon residues represented by R₃, R₉, R₁₂and R₁₈ in the above formulae include substituted and unsubstitutedradicals selected from ##STR7## and the like, wherein R₂₆ is asubstituted or unsubstituted monovalent hydrocarbon residue as describedherein and R₂₇ is a substituted or unsubstituted divalent hydrocarbonresidue as described herein.

Of course, it is to be further understood that the hydrocarbon residuesin the above formulae may also be substituted with any permissiblesubstituent. Illustrative substituents include radicals containing from1 to 18 carbon atoms such as alkyl, aryl, aralkyl, alkaryl andcycloalkyl radicals; alkoxy radicals; silyl radicals such as --Si(R₂₈)₃and --Si(OR₂₈)₃, amino radicals such as --N(R₂₈)₂ ; acyl radicals suchas --C(O)R₂₈ ; acyloxy radicals such as --OC(O)R₂₈ ; carbonyloxyradicals such as --COOR₂₈ ; amido radicals such as --C(O)N(R₂₈)₂ and--N(R₂₈)COR₂₈ ; sulfonyl radicals such as --SO₂ R₂₈ ; sulfinyl radicalssuch as --SO(R₂₈)₂ ; thionyl radicals such as --SR₂₈ ; phosphonylradicals such as --P(O)(R₂₈)₂ ; as well as halogen, nitro, cyano,trifluoromethyl and hydroxy radicals and the like, wherein each R₂₈ canbe a monovalent hydrocarbon radical such as alkyl, aryl, alkaryl,aralkyl and cycloalkyl radicals, with the provisos that in aminosubstituents such as --N(R₂₈)₂, each R₂₈ taken together can alsocompromise a divalent bridging group that forms a heterocyclic radicalwith the nitrogen atom, in amido substituents such as --C(O)N(R₂₈)₂ and--N(R₂₈)COR₂₈, each R₂₈ bonded to N can also be hydrogen, and inphosphonyl substituents such as --P(O)(R₂₈)₂, one R₂₈ can by hydrogen.It is to be understood that each R₂₈ group in a particular substituentmay be the same or different. Such hydrocarbon substituent radicalscould possibly in turn be substituted with a permissible substituentsuch as already herein outlined above.

Preferred alkylene oxides which can provide random or block oxyalkyleneunits in the complex hydrophobe compounds represented by formulae (i)and (ii) include alkylene oxides such as ethylene oxide, propyleneoxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2- and 2,3-pentyleneoxide, cyclohexylene oxide, 1,2-hexylene oxide, 1,2-octylene oxide,1,2-decylene oxide, and higher alpha-olefin epoxides; epoxidized fattyalcohols such as epoxidized soybean fatty alcohols and epoxidizedlinseed fatty alcohols; aromatic epoxides such as styrene oxide and2-methylstyrene oxide; and hydroxy- and halogen-substituted alkyleneoxides such as glycidol, epichlorohydrin and epibromohydrin. Thepreferred alkylene oxides are ethylene oxide and propylene oxide. Alsoincluded can be hydrocarbon residues from substituted and unsubstitutedcyclic esters or ethers such as oxetane and tetrahydrofuran. It isunderstood that the compounds represented by formulae (i) and (ii)herein can contain random and/or block oxyalkylene units as well asmixtures of oxyalkylene units. It is further understood that each R₄,R₅, R₁₀, R₁₃ and R₁₉ group in a particular substituent for all positivevalues of x, y, f, g and j respectively can be the same or different.

The values of x, y, z, f, g and j are not narrowly critical and can varyover a wide range. For example, the values of x, y, z, f, g and j canrange from 0 to about 200 or greater, preferably from about 0 to about100 or greater, and more preferably from about 0 to about 50 or greater.Any desired amount of alkylene oxide can be employed, for example, from0 to about 90 weight percent or greater based on the weight of thecomplex hydrophobe compound.

Referring to the general formulae (i) and (ii) above, it is appreciatedthat when R₁, R₂, R₇ and/or R₈ are a hydrocarbon residue of formulae(iii) above, the resulting compound may include any permissible numberand combination of hydrophobic groups of the dendritic or cascadingtype. Such compounds included in the above general formulae should beeasily ascertainable by one skilled in the art. Illustrative complexhydrophobe compounds having at least one active hydrogen useful in thisinvention and processes for preparation thereof are disclosed incopending U.S. patent application Ser. No. 07/887,648, which isincorporated herein by reference.

In a preferred embodiment of this invention, the structure shown informula (iii) can be a residue of the reaction product betweenepichlorohydrin and an alcohol, including those alcohols whose residuescan be described by formula (iii), or a phenolic, or a mixture thereof.The structures which result can be described as complex hydrophobes of adendritic or of a cascading nature. Pictorially, they can be describedas shown below: ##STR8##

Preferred macromonomer compounds useful in this invention include thoserepresented by the formulae: ##STR9## wherein R¹, R², R⁴, R₁₉, z and jare as defined herein.

The macromonomer compounds useful in this invention can undergo furtherreaction(s) to afford desired derivatives thereof. Such permissiblederivatization reactions can be carried out in accordance withconventional procedures known in the art. Illustrative derivatizationreactions include, for example, esterification, etherification,alkoxylation, amination, alkylation, hydrogenation, dehydrogenation,reduction, acylation, condensation, carboxylation, oxidation, silylationand the like, including permissible combinations thereof. This inventionis not intended to be limited in any manner by the permissiblederivatization reactions or permissible derivatives of macromonomercompounds.

More particularly, the hydroxyl-terminated macromonomer compounds ofthis invention can undergo any of the known reactions of hydroxyl groupsillustrative of which are reactions with acyl halides to form esters;with ammonia, a nitrile, or hydrogen cyanide to form amines; with alkylacid sulfates to form disulfates; with carboxylic acids and acidanhydrides to form esters and polyesters; with alkali metals to formsalts; with ketenes to form esters; with acid anhydrides to formcarboxylic acids; with oxygen to form aldehydes and carboxylic acids;ring-opening reactions with lactones, tetrahydrofuran; dehydrogenationto form aldehydes, isocyanates to form urethanes, and the like.

The monoethylenically unsaturated macromonomer component is subject toconsiderably variation within the formula presented previously. Theessence of the macromonomer is a complex hydrophobe carrying apolyethoxylate chain (which may include some polypropoxylate groups) andwhich is terminated with at least one hydroxy group. When thehydroxy-terminated polyethoxylate complex hydrophobe used herein isreacted with a monoethylenically unsaturated monoisocyanate, forexample, the result is a monoethylenically unsaturated urethane in whicha complex hydrophobe polyethoxylate structure is associated with acopolymerizable monoethylenic group via a urethane linkage.

The monoethylenically unsaturated compound used to provide themonoethylenically unsaturated macromonomer is subject to wide variation.Any copolymerizable unsaturation may be employed, such as acrylate andmethacrylate unsaturation. One may also use allylic unsaturation, asprovided by allyl alcohol. These, preferably in the form of ahydroxy-functional derivative, as is obtained by reacting a C₂ -C₄monoepoxide, like ethylene oxide, propylene oxide or butylene oxide,with acrylic or methacrylic acid to form an hydroxy ester, are reactedin equimolar proportions with an organic compound, such as toluenediisocyanate or isophorone diisocyanate. The preferred monoethylenicmonoisocyanate is styryl, as in alpha, alpha-dimethyl-m-isopropenylbenzyl isocyanate. Other suitable organic compounds include, forexample, monoethylenically unsaturated esters, ethers, amides, ureas,anhydrides, other urethanes and the like.

The polymers of this invention can be prepared via a variety ofpolymerization techniques known to those skilled in the art. Thetechnique of polymerization influences the microstructure, monomersequence distribution in the polymer backbone and its molecular weightto influence the performance of the polymer. Illustrative polymerizationtechniques include, for example, conventional and staged emulsionpolymerization via batch, semi-continuous, or continuous processes,micellar polymerization, inverse emulsion polymerization, solutionpolymerization, non-aqueous dispersion polymerization, interfacialpolymerization, emulsion polymerization, suspension polymerization,precipitation polymerization, addition polymerizations such as freeradical, anionic, cationic or metal coordination methods, and the like.

The thickeners of this invention possess structural attributes of twoentirely different types of thickeners (those which thicken by alkalisolubilization of a high molecular weight entity, and those whichthicken due to association), and this may account for the superiorthickener properties which are obtained herein.

The aqueous emulsion copolymerization is entirely conventional. Toobtain an estimate of thickening efficiency, the product can be dilutedwith water to about 1% solids content and then neutralized with alkali.The usual alkali is ammonium hydroxide, but sodium and potassiumhydroxide, and even amines, like triethylamine, may be used forneutralization. The neutralized product dissolves in the water toprovide an increase in the viscosity. In the normal mode of addition,the unneutralized thickener is added to a paint and then neutralized.This facilitates handling the thickener because it has a lower viscositybefore neutralization. This procedure also makes more water availablefor the paint formulation.

The polymers of this invention are preferably produced by conventionalaqueous emulsion polymerization techniques, using appropriateemulsifiers for emulsifying the monomers and for maintaining the polymerobtained in a suitable, dispersed condition. Commonly used anionicsurfactants such as sodium lauryl sulfate, dodecylbenzene sulfonate andethoxylated fatty alcohol sulfate can be used as emulsifiers. Theemulsifier may be used in a proportion of 1/2 to 6% of the weightmonomers.

Preferably, water-soluble initiators such as alkali metal or ammoniumpersulfate are used in amounts from 0.01 to 1.0% on the weight ofmonomers. A gradual addition thermal process employed at temperaturesbetween 60° C. to 100° C. is preferred over redox systems.

The polymerization system may contain small amounts (0.01 to 5% byweight, based on monomer weight) of the chain transfer agent mercaptanssuch as hydroxyethyl mercaptan, β-mercaptopropionic acid and alkylmercaptans containing from about 4 to 22 carbon atoms, and the like. Theuse of mercaptan modifier reduces the molecular weight of the polymerand therefore its thickening efficiency.

The polymers of this invention may further be modified by introducing anamount of component (D), namely, one or more polyethylenicallyunsaturated copolymerizable monomers effective for crosslinking, such asdiallylphthalate, divinylbenzene, allyl methacrylate, trimethylolpropane triacrylate, ethyleneglycol diacrylate or dimethacrylate,1,6-hexanediol diacrylate or dimethylacrylate, diallyl benzene, and thelike. Thus, from about 0.05 or less to about 20% or greater of suchpolyethylenically unsaturated compound based on total weight of monomermay be included in the composition forming the polymer. The resultingpolymers are either highly branched or in the form of three-dimensionalnetworks. In the neutralized salt form, those networks swell in anaqueous system to act as a highly efficient thickener.

Other illustrative polyethylenically unsaturated monomers useful in thisinvention include, for example, any copolymerizable compound whichcontains two or more nonconjugated points of ethylenic unsaturation ortwo or more nonconjugated vinylidene groups of the structure, CH₂ ═C═,such as divinyltoluene, trivinylbenzene, divinylnaphthalene,trimethylene glycol diacrylate or dimethacrylate,2-ethylhexane-1,3-dimethyacrylate, divinylxylene, divinylethylbenzene,divinyl ether, divinyl sulfone, allyl ethers of polyhdric compounds suchas of glycerol, pentaerythritol, sorbitol, sucrose and resorcinol,divinylketone, divinylsulfide, allyl acrylate, diallyl maleate, diallylfumarate, diallyl phthalate, diallyl succinate, diallyl carbonate,diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate,diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallylaconitate, triallyl citrate, triallyl phosphate,N,N-methylenediacrylamide, N,N'-methylenedimethacrylamide,N,N'-ethylidenediacrylamide and1,2-di-(α-methylmethylenesulfonamide)-ethylene.

The polymer may be utilized in a variety of ways to provide thethickener or thickened compositions of this invention. For example, thepolymer, while in aqueous dispersion or dry form, may be blended into anaqueous system to be thickened followed by addition of a neutralizingagent. Alternatively, the polymer may first be neutralized in aqueousdispersion form and then blended with the aqueous system. Preferably, ifco-thickening by a surfactant is desired, the components are separatelyblended (as dry components or as dispersions or slurries) into anaqueous dispersion to be thickened, followed by the neutralization step.Although aqueous concentrates of the polymer in acid form and thesurfactant may be formed and added to an aqueous dispersion to bethickened as needed, followed by neutralization, such concentrates tendto be too viscous for easy handling. It is nevertheless possible toprepare either a dry blend or an aqueous, high solids composition whichis sufficiently low in viscosity as to be pumpable or pourable, and thento further thicken the admixture by addition of an alkaline material.

The polymer thickener may be provided in a dry state in number of ways.For example, the unneutralized polymer may be spray or drum dried and,if desired, blended with a surfactant co-thickener. However, it is alsopossible to spray dry or otherwise dehydrate the neutralized polymerthickener, and then reconstitute the aqueous thickener dispersion at afuture time and place by agitation in a aqueous medium, provided the pHof the dispersion is maintained at pH 7 or higher.

The more usual method of application of the dispersion of this inventionfor aqueous thickening is to add the aqueous dispersion of the polymerto the medium to be thickened and, after mixing, to introduce analkaline material to neutralize the acid. The major portion of thethickening effect is obtained in a few minutes upon neutralization. Inthe presence of high concentrations of electrolytes, the viscositydevelopment may take much longer. This method of applying a polymer toan aqueous system before neutralization enables one to handle a highsolids thickener in a non-viscous state, to obtain uniform blend, andthen to convert to a highly viscous condition by the simple addition ofan alkaline material to bring the pH of the system to 7 or above.

The aqueous solutions thickened with the neutralized polymers of thisinvention exhibit good viscosity stability even at a pH as high as 13.

The polymer may be used to thicken compositions under acidic conditionsin the presence of a relatively large amount of surfactants wherein thethickened composition, for example, an aqueous system, has a pH below 7,even as low as 1.

An enhancement of thickening (herein termed "co-thickening") can resultupon the addition of a surfactant to an aqueous system containing thepolymer of this invention, when the polymer is neutralized. In somecases the thickening can be enhanced up to about 40 times the viscosityafforded by the neutralized polymer alone. A wide range of surfactantsmay be used. Although trace amounts of surfactant may be residuallypresent from the polymerization of the monomers comprising the polymer(for example, whatever may remain of the about 1.5 weight percentsurfactant on monomers), such amounts of surfactant are not believed toresult in any measurable co-thickening.

On the basis of an aqueous system containing about 0.1 to 5% by weightof polymer solids, a useful amount of surfactant for optimumco-thickening is about 0.1 to 1.0% by weight of the total system. Asindicated, the amounts of polymer and surfactant co-thickener may varywidely, even outside these ranges, depending on polymer and surfactanttype and other components of the aqueous system to be thickened.However, the co-thickening can reach a maximum as surfactant is addedand then decreases as more surfactant is added. Hence, it may beuneconomical to employ surfactant in amounts outside the statedconcentrations and polymer/surfactant ratios, but this can be determinedin a routine manner in each case.

The preferred method of application of the polymer and the surfactantfor aqueous thickening is to add in any sequence the polymer and thesurfactant to the medium to be thickened and, after mixing, to introducean alkaline material to neutralize the acid. This method of applyingpolymer and surfactant to an aqueous system before neutralizationenables one to handle a high solids thickener in a non-viscous state, toobtain a uniform blend, and then to convert to a highly viscouscondition by the simple addition of an alkaline material to bring the pHof the system to 7 or above. However, the polymer in the aqueous systemmay also be neutralized before addition of the surfactant.

The surfactants which may be used include nonionics and anionics, singlyor in combination, the selection necessarily depending uponcompatibility with other ingredients of the thickened or thickenabledispersions of this invention. Cationic and amphoteric surfactants mayalso be used provided they are compatible with the polymer and otheringredients of the aqueous system, or are used in such small amounts asnot to cause incompatibility.

Suitable anionic surfactants that may be used include the higher fattyalcohol sulfates such as the sodium or potassium salt of the sulfates ofalcohols having from 8 to 18 carbon atoms, alkali metal salts or aminesalts of high fatty acid having 8 to 18 carbon atoms, and sulfonatedalkyl aryl compounds such as sodium dodecyl benzene sulfonate. Examplesof nonionic surfactants include alkylphenoxypolyethoxyethanols havingalkyl groups of about 7 to 18 carbon atoms and about 9 to 40 or moreoxyethylene units such as octylphenoxypolyethoxyethanols,dodecylphenoxypolyethoxyethanols; ethylene oxide derivatives oflong-chain carboxylic acids, such as lauric, myristic, palmitic, oleic;ethylene oxide condensates of long-chain alcohols such as lauryl orcetyl alcohol, and the like.

Examples of cationic surfactants include lauryl pyridinium chloride,octylbenzyltrimethylammonium chloride, dodecyltrimethylammonium chloridecondensates of primary fatty amines and ethylene oxide, and the like.

The foregoing and numerous other useful nonionic, anionic, cationic, andamphoteric surfactants are described in the literature, such asMcCutcheon's Detergents & Emulsifiers 1981 Annual, North AmericaEdition, MC Publishing Company, Glen Rock, N.J. 07452, U.S.A.,incorporated herein by reference.

In general, solvents and non-solvents (or mixtures of solvents,non-solvents, other organics and volatiles) can be used to manipulatethe viscosity of polymer containing systems. In the examples herein, itis interesting to note how mineral spirits act like co-thickener, andhow the water solubility of the other solvent influences how muchmineral spirits can be added before the solution separates into a twophase system. The co-thickening with mineral spirits has utility intextile printing pastes, and in waterborne automotive basecoats. Thesesystems usually contain mineral spirits (because of the pigments usedtherein), so that the mineral spirits provide an economical way ofincreasing viscosity and improving the efficiency of the thickener.

The amount of the polymer that may be dissolved in any given aqueouscomposition may fall within a wide range depending on the particularviscosity desired.

Thus, although any effective amount of the polymer may be employed fordissolution, typically from about 0.05 to about 20%, preferably fromabout 0.1 to about 5%, and most preferably from about 0.1 to about 3% byweight, based on the weight of the final aqueous composition includingpolymer is used.

For latex paint compositions, the polymer may be dissolved therein in anamount of from about 0.05 to about 5%, and preferably from about 0.1 toabout 3% by weight, based on the weight of the total compositionincluding polymer.

The polymers of this invention may be employed as thickeners forcontrolling viscosity of any aqueous based composition. An aqueous basedcomposition is an aqueous composition as herein defined to be acomposition wherein water comprises at least 10% by weight of the totalcomposition (including 100% water).

For example, aqueous dispersions, emulsions, suspensions, solutions,slurries and the like, may be thickened by the polymers of thisinvention.

Typical aqueous compositions include compositions to be applied totextiles such as latex adhesives, warp sizes, backings for rugs andother pile fabrics. The polymer may also be used when thickening isdesired in the purification of raw water such as the saline water usedin the recovery of oil from exhausted oil wells by water floodingtechniques. Other aqueous coatings compositions to which the polymer canbe added for thickening purposes include drilling muds, caulks,adhesives, coating compositions such as paper coatings, furniturefinishes, ink compositions, latex paints, foundary core washes, and thelike.

Preferably, the polymer is used to thicken aqueous coating compositions,and more preferably latex paint compositions.

Examples of suitable latex paint compositions include those based onresins or binders of acrylonitrile, copolymers of acrylonitrile whereinthe comonomer is a diene like isoprene, butadiene or chloroprene,homopolymers of styrene, homopolymers and copolymers of vinyl halideresins such as vinyl chloride, vinylidene chloride or vinyl esters suchas vinyl acetate, vinyl acetate homopolymers and copolymers, copolymersof styrene and unsaturated acid anhydrides like maleic anhydrides,homopolymers and copolymers of acrylic and methacrylic acid and theiresters and derivatives, polybutadiene, polyisoprene, butyl rubber,natural rubber, ethylene-propylene copolymers, olefins resins likepolyethylene and polypropylene, polyvinyl alcohol, carboxylated naturaland synthetic latices, epoxies, epoxy esters and similar polymeric latexmaterials.

Latex paint compositions are well known in the art and typicallycomprise an emulsion, dispersion or suspension of discrete particles ofresin binder and pigment in water. Optional ingredients typicaly includethickeners, antifoam agents, plasticizers, surfactants, coalescingagents, and the like.

The polymers described herein are useful in a variety of aqueoussystems, such as textile coatings (woven and nonwoven), latex paintformulations, cosmetic formulations, pigment dispersions and slurries,dentrifrices, hand lotions, liquid detergents, quenchants, agriculturalchemicals, concrete additives, transmission fluids, waste watertreatment (flocculants), turbulent drag reduction, aircraft anti-icing,automation coatings (OEM and refinish), architectural coatings,industrial coatings and the like.

As used herein, the term "complex hydrophobe" is contemplated to includeall permissible hydrocarbon compounds having 2 or more hydrophobegroups, e.g., bis-dodecylphenyl, bis-nonylphenyl, bis-octylphenyl andthe like.

For purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. In a broad aspect, the permissible hydrocarbons includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic organic compounds which can besubstituted or unsubstituted.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds unless otherwiseindicated. In a broad aspect, the permissible substituents includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic substituents of organiccompounds. Illustrative substituents include, for example, alkyl,alkyloxy, aryl, aryloxy, hydroxy, hydroxyalkyl, amino, aminoalkyl,halogen and the like in which the number of carbons can range from 1 toabout 20 or more, preferably from 1 to about 12. The permissiblesubstituents can be one or more and the same or different forappropriate organic compounds. This invention is not intended to belimited in any manner by the permissible substituents of organiccompounds.

The invention is illustrated by certain of the following examples.

EXAMPLE 1 Preparation of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, two liter round bottom flask equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser were added 220 grams (1.00mole) of nonylphenol and 250 milliliters of cyclohexane. The solutionwas then heated to reflux and 2.8 grams (1.3 wt. % based on nonylphenol)of potassium hydroxide in 10 milliliters of water was slowly added tothe flask. After essentially all the water was recovered in thedecanting head (10 milliliters+1 milliliter formed), 250.7 grams (0.91mole) of nonylphenyl glycidyl ether as added dropwise. During theaddition of the glycidyl ether, the reaction temperature was maintainedbetween 60° and 80° C. After the addition was complete, the solution wasrefluxed for four hours. The contents of the flask were then washed witha five percent aqueous solution of phosphoric acid, and the organiclayer was separated from the water layer and washed twice with deionizedwater. The reaction mixture was then placed in a one liter round bottomflask, and the remaining cyclohexane and unreacted nonylphenol wererecovered by distillation, first at atmospheric pressure, then undervacuum at 0.2 mm Hg. The kettle temperature was not allowed to exceed180° C. during the distillation to prevent discoloration of the product.The concentrated solution was then refiltered to give 425 grams of apale-yellow liquid. End-group MW analysis gave a molecular weight of506.8 (theoretical MW=496.8). Ir and nmr spectra were identical topreviously recorded spectra for the compound.

EXAMPLE 2 Preparation of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, two liter round bottom flask, equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser, were added 300 millilitersof cyclohexane and 451.7 grams (2.05 mole) of nonylphenol. The solutionwas then heated to reflux and 58.9 grams (1.05 mole) of potassiumhydroxide in 60 milliliters of water was slowly added via the additionfunnel. After essentially all the water was recovered in the decantinghead (60 milliliter+19 milliliters formed), the reaction was cooled to40° C., and 92.5 grams (1.00 mole) of epichlorohydrin was slowly added.During the addition, the reaction temperature was maintained below 60°C. by controlling the rate of epichlorohydrin addition. After all theepichlorohydrin was added, the solution was allowed to stir for onehour, and then brought to reflux for an additional three hours. Thereaction mixture was then filtered under vacuum through a steam-jacketedBuchner funnel to remove the potassium chloride formed as a by-product.The filtration process was performed a total of three times to removethe majority of the salts. The reaction mixture was then placed in a oneliter round bottom flask, and the remaining cyclohexane and unreactednonylphenol were recovered by distillation, first at atmosphericpressure, then under vacuum at 0.2 mm Hg. The kettle temperature was notallowed to exceed 180° C. during the distillation to preventdiscoloration of the product. The concentrated solution was thenrefiltered to give 275 grams of a pale-yellow liquid. End-group MWanalysis gave a molecular weight of 459.7 (theoretical MW=496.8). Ir andnmr spectra were identical to previously recorded spectra for thecompound.

EXAMPLE 3 Preparation of 5 Mole Ethoxylate of1,3-Bis(nonylphenoxy)-2-propanol

To a 500 milliliter, stainless steel, high pressure autoclave wascharged 200 grams (0.40 mole) of 1,3-bis(nonylphenoxy)-2-propanol, whichcontained a catalytic amount of the potassium salt of the alcohol asdescribed in Example 1. After purging the reactor with nitrogen, thealcohol was heated to 130° C. with stirring, and 86.9 grams (2.0 mole)of ethylene oxide was added over a two hour period. The reactiontemperature and pressure were maintained from 130° C. to 140° C. and 60psig during the course of the reaction. After the addition of ethyleneoxide was complete, the reaction mixture was held at 140° C. for anadditional hour to allow all the ethylene oxide to cook out. Thereaction mixture was dumped while hot, under nitrogen, and neutralizedwith acetic acid to yield 285 grams of a pale-yellow liquid.

EXAMPLE 4 Preparation of Adduct of Nonylphenyl Glycidyl Ether and 5 MoleEthoxylate of 1,3-Bis(nonylphenoxy)-2-propanol

To a five neck, one liter, round bottom flask equipped as in Example 1was added 119.8 grams (0.17 mole) of the 5 mole ethoxylate of1,3-bis(nonylphenoxy)-2-propanol and 100 milliliters of cyclohexane. Themixture was refluxed (100° C.) for one hour to remove residual water,and then cooled to 50° C. under nitrogen to add 0.5 grams of BF₃ /Et₂ O.Nonylphenyl glycidyl ether (46.0 grams, 0.17 mole) was then added to theflask over a one hour period, and the reaction was heated to reflux.After three hours at reflux, the reaction mixture was transferred to aseparatory funnel, while hot, and washed with a saturated aqueoussolution of sodium bicarbonate. The organic layer was separated from thewater layer, and washed twice with hot deionized water. The washes wereperformed at 50° C. to facilitate the separation of the two layers. Thewater and cyclohexane were then evaporated from the organic layer, undervacuum, to yield 145 grams of a pale-yellow, viscous liquid. End-groupmolecular weight analysis gave a molecular weight of 880 (theoreticalmolecular weight=993).

EXAMPLE 5 Preparation of Poly(nonylphenol glycidyl ether)

To a 500 milliliter round bottom equipped with an overhead stirrer,nitrogen inlet, reflux condenser, additional funnel, and temperaturecontroller was charged 1.9 grams of ethanol (22 mmoles) and 200 grams ofcyclohexane. The solution was brought to 50° C. Once heated, 0.5milliliters (4 mmoles) of BF₃ /Et₂ O was added using a 2 millilitersyringe. Once the acid was added, 100.0 grams of nonylphenol glycidylether (362 mmoles) was added dropwise so as to maintain a reactiontemperature of 45° C.-55° C. Once the glycidyl ether was added, thesolution is refluxed for 3 hours, then cooled to about 50° C.

While hot (<60° C.) the organic was transferred to a separatory funneland was washed once with 100 milliliters of 5% sodium bicarbonatesolution. The aqueous layer was drained and the organic was washed twomore times with 100 milliliter portions of deionized water. The aqueouslayers were decanted and the organic was dried for at least 1 hour overmagnesium sulfate. Once dry the magnesium sulfate was filtered from theorganic which was stripped of solvent using a rotary evaporator. Thefinal yield of viscous polymer was 100 grams. The GPC molecular weightwas Mw=2600 and the Mn=1700 based on monodisperse polystyrene standards.

EXAMPLE 6 Ethoxylation of Poly(nonylphenol glycidyl ether)

To a 500 milliliter stainless steel Zipperclave was added 60.0 grams(0.035 moles based on an approximate molecular weight of 1700 gram/mole)of the resin prepared in Example 5 along with 0.5 grams of potassiumhydroxide. The vessel was attached to an automated ethoxylation unit andwas heated to 50° C. The vessel was continuously purged with nitrogenfor 15 minutes and was then heated to 100° C. where it was againcontinuously purged with nitrogen for another 15 minutes. The vessel wasthen heated to 140° C. and was given a series of 6 purges by pressuringthe vessel up to 80 psi, and then venting. Once the venting process wascomplete, the vessel was pressured to 20 psi with nitrogen.

The ethylene oxide lines were opened to the motor valves along with themain feed line on the Zipperclave. The feed was continued and the vesselpressure was regulated at 55 psi and a temperature of 140° C. Theautomation was designed to hold the temperature and the pressure withinsafe operating limits while addition of ethylene oxide proceeded througha pair of motor control valves. The feed was allowed to continue until60.0 grams of ethylene oxide (1.362 moles) was added based on adifference weight of the feed cylinder. After the feed was complete, thereaction was allowed to continue for 1 hour after which the vessel wascooled to 60° C., purged 4 times with nitrogen to 80 psi and was dumpedto a container. The final product yield was 115 grams with a theoreticalyield of 120 grams. The GPC molecular weight of the product was Mw=3550and the MN=2930 based on monodisperse polystyrene standards.

EXAMPLE 7 Preparation of Poly(phenyl glycidyl ether)

To a 500 milliliter round bottom equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged 47.06 grams of phenol (500 mmoles) and 100 gramsof toluene. The solution was brought to 50° C. Once heated, 1.0milliliter (8 mmoles) of BF₃ /Et₂ O was added using a 2 millilitersyringe. Once the acid was added, 68.18 grams of phenyl glycidyl ether(454 mmoles) was added dropwise so as to maintain a reaction temperatureof 45° C.-55° C. Once the glycidyl ether was added, the solution isrefluxed for 3 hours, then cooled to about 50° C.

While hot (<60° C.) the organic was transferred to a separatory funneland was washed once with 100 milliliters of 5% sodium bicarbonatesolution. The aqueous layer was drained and the organic was washed twomore times with 100 milliliter portions of deionized water. The aqueouslayers were decanted and the organic was dried for at least 1 hour overmagnesium sulfate. Once dry the magnesium sulfate was filtered from theorganic which was stripped of solvent using a rotary evaporator. Thefinal yield of viscous polymer was 90.3 grams (with 11% unreactedphenol). The GPC molecular weight was Mw=470 and the Mn=310 (on averagea trimer) based on monodisperse polystyrene standards.

EXAMPLE 8 Preparation of 1,3-Bis(phenoxy)-2-propanol using the CascadingPolyol Technique

To a 1 liter round bottom flask equipped with an overhead stirrer,nitrogen inlet, reflux condenser, addition funnel, and temperaturecontroller was charged 94.11 grams of phenol (1 mole), 12.86 grams oftetraethylammonium iodide (0.05 moles), 3.00 grams of water (0.17moles), 42.08 grams of potassium hydroxide (0.75 moles), and 250 gramsof toluene. To a 100 milliliter additional funnel was charged 23.13grams of epichlorohydrin (0.25 moles) and 50 grams of toluene. Thesolution was brought to 65° C. at which time the epichlorohydrinsolution was added over a period of 15 minutes while maintaining areaction temperature of 65° C.±5° C. The reaction was allowed to proceedfor 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliters portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed along with unreacted phenol using a rotary evaporator. Thefinal yield of product was 64.5 grams which was 106% of theory (residualis phenol). Final product purity was about 95% as shown by GPC.

EXAMPLE 9 Dimerization of 1,3-Bis(phenoxy)-2-propanol using theCascading Polyol Technique

To a 250 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, additional funnel, andtemperature controller was charged 20.03 grams of1,3-bis-(phenoxy)-2-propanol prepared in Example 8 (82 mmoles), 2.06grams of tetraethylammonium iodide (8 mmoles), 0.49 grams of water (27mmoles), 6.51 grams of potassium hydroxide (116 mmoles), and 125 gramsof toluene. To a 100 milliliter addition funnel was charged 3.61 gramsof epichlorohydrin (39 mmoles) and 25 grams of toluene. The solution wasbrought to 65° C. at which time the epichlorohydrin solution was addedover a period of 15 minutes while maintaining a reaction temperature of65° C.±5° C. The reaction was allowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliter portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed using a rotary evaporator. The final yield of product was21.6 grams which was 101% of theory. GPC showed two major components ofthe product. The first was the starting material at about 41% (Mn=220)and the second was the coupled product at about 59% (Mn=520).

EXAMPLE 10 Preparation of 1,3-Bis(hexadecyloxy)-2-propanol using theCascading Polyol Technique

To a 500 milliliter round bottom flask equipped with an overheadstirrer, nitrogen inlet, reflux condenser, additional funnel, andtemperature controller was charged 60.61 grams of hexadecanol (0.25moles), 6.18 grams of tetraethylammonium iodide (0.024 moles), 1.44grams of water (0.082 moles), 20.20 grams of potassium hydroxide (0.36moles), and 125 grams of toluene. To a 100 milliliter addition funnelwas charged 11.10 grams of epichlorohydrin (0.12 moles) and 25 grams oftoluene. The solution was brought to 65° C. at which time theepichlorohydrin solution was added over a period of 15 minutes whilemaintaining a reaction temperature of 65° C.±5° C. The reaction wasallowed to proceed for 48 hours.

After 48 hours, the solution was cooled down to room temperature. Thetoluene solution was washed with two 250 milliliter portions ofdeionized water. The aqueous layers were drained off, and the toluenewas removed using a rotary evaporator. The final yield of product was70.9 grams which is 109% of theory (residual is hexadecanol).

EXAMPLE 11 Sulfation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀-block-(ethylene oxide)₁₀

To a 250 milliliter round bottom flask equipped with an overheadstirrer, a temperature controller, and a vacuum adapter was added 75.0grams of the material from Example 13 (49 mmoles). The kettle was thenevacuated to <20 mmHg and heated to 100° C. to remove any water. After 1hour, the kettle was cooled to 60° C. while under vacuum. When reaching60° C., vacuum was broken with nitrogen and 5.3 grams of sulfamic acid(54 mmoles) was added. After charging the sulfamic acid, the kettle washeated to 110° C. and evacuated to <20 mmHg. The reaction was allowed toproceed for 3 hours.

At the end of the hold period, the kettle was cooled to 85° C. andvacuum was broken with nitrogen. 1.2 grams of diethanolamine (11 mmoles)was slowly added under a blanket of nitrogen. This solution was stirredfor 30 minutes. 10 grams of ethanol was added to the kettle and thetemperature was regulated to 55° C. This solution was stirred for 30minutes. The heat was removed from the kettle and 30 grams of wateralong with 20 grams of ethanol were added while maintaining goodagitation. The solution was stirred for 15 minutes or until cooled toroom temperature (<35° C.).

The pH was checked by dissolving 2 grams of the product solution in 18grams of deionized water. If the pH was below 6.5, 0.2 gram incrementsof diethanolamine was added until the pH is between 6.5 and 7.5.

EXAMPLE 12 Preparation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀

To a 500 milliliter stainless steel Zipperclave was added 100.0 grams(0.202 moles) of 1,3-bis(nonylphenoxy)-2-propanol prepared in Example 1along with 0.7 grams of potassium hydroxide. The vessel was attached toan automated unit and was heated to 50° C. The vessel was continuouslypurged with nitrogen for 15 minutes and was then heated to 100° C. whereit was again continuously purged with nitrogen for another 15 minutes.The vessel was then heated to 140° C. and is given a series of 6 purgesby pressuring the vessel up to 80 psi, and then venting. Once theventing process was completed, the vessel was pressured to 20 psi withnitrogen.

Lines connected to a cylinder which had been precharged with 117.0 gramsof propylene oxide (2.02 moles) were opened to the motor valves alongwith the main feed line on the Zipperclave. The feed was continued andthe vessel pressure was regulated at 55 psi and a temperature of 140° C.The automation was designed to hold the temperature and the pressurewithin safe operating limits while addition of ethylene oxide proceededthrough a pair of motor control valves. The feed was allowed to continueuntil all of the propylene oxide had been fed. After the feed wascomplete, the reaction was allowed to continue for 1 hour after whichthe vessel was cooled to 60° C., purged 4 times with nitrogen to 80 psiand was dumped to a container. The final product yield was 211 gramswith a theoretical yield of 277 grams. The GPC molecular weight of theproduct was Mw=650 and the Mn=490 based on monodisperse polystyrenestandards.

EXAMPLE 13 Preparation of1,3-Bis(nonylphenoxy)-2-propanol-block-(propylene oxide)₁₀-block-(ethylene oxide)₁₀

To a 500 milliliter stainless steel Zipperclave was added 75.0 grams ofthe propoxylate prepared in Example 12 (0.070 moles) along with 0.3grams of potassium hydroxide. The vessel was attached to an automatedethoxylation unit and was heated to 50° C. The vessel was continuouslypurged with nitrogen for 15 minutes and was then heated to 100° C. whereit was again continuously purged with nitrogen for another 15 minutes.The vessel was then heated to 140° C. and was given a series of 6 purgesby pressuring the vessel up to 80 psi, and then venting. Once theventing process was completed, the vessel was pressured to 20 psi withnitrogen.

The ethylene oxide lines were opened to the motor valves along with themain feed line on the Zipperclave. The feed was continued and the vesselpressure was regulated at 55 psi and a temperature of 140° C. Theautomation was designed to hold the temperature and the pressure withinsafe operating limits while addition of ethylene oxide proceeded througha pair of motor control valves. The feed was allowed to continue until30.7 grams ethylene oxide (0.696 moles) was added based on a differenceweight of the feed cylinder. After the feed was complete, the reactionis allowed to continue for 1 hour after which the vessel was cooled to60° C., purged 4 times with nitrogen to 80 psi and was dumped to acontainer. The final product yield was 99 grams with a theoretical yieldof 106 grams.

EXAMPLE 14 Preparation of Bis(nonylphenoxy) Adduct of 1,4-ButanediolDiglycidyl Ether

To a five neck, two liter round bottom flask equipped with an additionfunnel, thermometer, nitrogen dispersant tube, mechanical stirrer, and adecanting head with a water-cooled condenser were added 506.8 grams(2.30 mole) of nonylphenol and 350 milliliters of cyclohexane. Thesolution was heated to reflux, and 6.5 grams (1.3 weight percent basedon nonylphenol) of potassium hydroxide in 15 milliliters of water wasslowly added to the round bottom flask. After all the water wasrecovered in the decanting head (15 milliliters+2 milliliters formed),220 grams (1.09 mole) of 1,4-butanediol diglycidyl ether was addeddropwise between 60 and 80° C. After the addition was complete, thesolution was refluxed for four hours. The contents of the flask werethen washed with a five percent aqueous solution of phosphoric acid, andthe organic layer was separated from the water layer and washed twicewith deionized water. The reaction mixture was then placed in a oneliter round bottom flask, and the remaining cyclohexane and unreactednonylphenol were recovered by distillation, first at atmosphericpressure, then under vacuum at 0.2 mm Hg. The kettle temperature was notallowed to exceed 180° C. during the distillation to preventdiscoloration of the product. The concentrated solution was thenrefiltered to give 710 grams of a pale-yellow liquid. Molecular weightby end-group MW analysis was 689.9 (theoretical MW=643.0). Ir and nmrspectra were consistent with the expected structure of the product.

EXAMPLE 15 Preparation of 3 Mole Ethoxylate of1,3-Bis(nonylphenoxy)-2-propanol

To a five hundred milliliter Zipperclave reactor were charged, undernitrogen, 200.1 grams (0.43 mole) of 1,3-bis(nonylphenoxy)-2-propanolprepared in Example 2 and 0.20 grams (0.1 weight percent) of BF₃.Et₂ O.The reaction mixture was heated to 80° C., and 55.1 grams (1.25 mole) ofethylene oxide was fed to the reactor over a two hour period. After allthe ethylene oxide was fed, the reaction mixture was allowed to cook outfor one hour and then dumped hot, under nitrogen, into a jar containing160 milliliters of a one percent aqueous solution of sodium hydroxide.The organic layer was separated from the water layer and washed twicewith deionized water. The washes were performed at 90° C. to facilitatethe separation of the two layers. The product was then dried byazeotropic removal of the water, using cyclohexane (300 milliliters) asthe entrainer. The cyclohexane was stripped off under vacuum to give apale-yellow liquid with a molecular weight by end-group MW analysis of601.7 (theoretical MW=629). Ir and nmr spectra were consistent with theexpected structure of the product.

EXAMPLE 16 Preparation of 8 Mole Ethoxylate of Bis(nonylphenoxy) Adductof 1,4-Butanediol Diglycidyl Ether

To a five hundred milliliter Zipperclave reactor were charged, undernitrogen, 150.2 grams (0.22 mole) of bis(nonylphenoxy) adduct of1,4-butanediol diglycidyl ether prepared in Example 14 and 0.30 grams(0.2 weight percent) of BF₃.Et₂ O. The reaction mixture was heated to80° C., and 77.5 grams (1.76 mole) of ethylene oxide was fed to thereactor over a two hour period. After all the ethylene oxide was fed,the reaction mixture was allowed to cook out for one hour and thendumped hot, under nitrogen, into a jar containing 160 milliliters of aone percent aqueous solution of sodium hydroxide. The organic layer wasseparated from the water layer and washed twice with deionized water.The washes were performed at 90° C. to facilitate the separation of thetwo layers. The product was then dried by azeotropic removal of thewater, using cyclohexane (300 milliliters) as the entrainer. Thecyclohexane was stripped off under vacuum to give a pale-yellow liquidwith a molecular weight by end-group MW analysis of 1047 (theoreticalMW=995). Ir and nmr spectra were consistent with the expected structureof the product.

EXAMPLE 17 Preparation of Macromonomer Compound

Into a 1 liter round bottom reaction flask equipped with a heatingmantle, dean stark trap, condenser, thermometer, nitrogen bubbler,nitrogen purge line and stirrer was charged 300 grams of toluene and 63grams of a surfactant identified as S-1 in Table A below. With nitrogenpurge, the resulting solution was heated to reflux at approximately 110°C. and azeotroped to remove trace water to dryness. The solution wassubsequently cooled to 90° C., and 1.5 grams of bismuth hex chem 28%bismuth octoate catalyst (Mooney Chemical, Inc., Cleveland, Ohio) wascharged and allowed to mix well, after which a stoichiometric amount of95% m-TMI aliphatic isocyanate (American Cyanamid, Stamford, Conn.) wascharged. After the reaction proceeded at 90° C. for 1.3 hours, theresulting product was cooled to 70° C. and 0.03 grams of2,6-di-tert-4-methyl phenol (BHT) preservative was added. The mixturewas poured into a stainless steel pan with large surface area tofacilitate drying. The final product was a waxy material, and isdesignated herein as macromonomer M-1.

                  TABLE A                                                         ______________________________________                                         ##STR10##                                                                                                     Moles of                                     Surfactant                                                                            R.sub.1     R.sub.2 /R.sub.3                                                                           Ethoxylation                                 ______________________________________                                        S-1     Nonylphenol Hydrogen (R.sub.2)                                                                         40                                           S-2     Nonylphenol Nonylphenol (R.sub.3)                                                                      40                                           S-3     Nonylphenol Nonylphenol (R.sub.3)                                                                      20                                           S-4     Nonylphenol Octylphenol (R.sub.3)                                                                      20                                           S-5     Nonylphenol Octylphenol (R.sub.3)                                                                      40                                           S-6     Nonylphenol Nonylphenol (R.sub.3)                                                                      80                                           S-7     Nonylphenol Nonylphenol (R.sub.3)                                                                      120                                          ______________________________________                                    

EXAMPLES 18-34 Preparation of Macromonomer Compounds

In a manner similar to that described in Example 17, other macromonomerswere prepared using stoichiometric amounts of the surfactants andunsaturated compounds identified in Table B below.

                  TABLE B                                                         ______________________________________                                        Example          Unsaturated     Macromonomer                                 No.    Surfactant                                                                              Compound        Designation                                  ______________________________________                                        18     S-2       m-TMI           M-2                                          19     S-3       m-TMI           M-3                                          20     S-4       m-TMI           M-4                                          21     S-5       m-TMI           M-5                                          22     S-6       m-TMI           M-6                                          23     S-7       m-TMI           M-7                                          24     S-2       Isocyanato Ethyl                                                                              M-8                                                           Methacrylate                                                 25     S-5       Isocyanato Ethyl                                                                              M-9                                                           Methacrylate                                                 26     S-1       Methacrylic Anhydride                                                                          M-10                                        27     S-2       Methacrylic Anhydride                                                                          M-11                                        28     S-5       Methacrylic Anhydride                                                                          M-12                                        29     S-6       Methacrylic Anhydride                                                                          M-13                                        30     S-2       Acrylic Anhydride                                                                              M-14                                        31     S-5       Acrylic Anhydride                                                                              M-15                                        32     S-6       Acrylic Anhydride                                                                              M-16                                        33     S-2       Crotonic Anhydride                                                                             M-17                                        34     S-5       Maleic Anhydride                                                                               M-18                                        ______________________________________                                    

EXAMPLE 35 Preparation of Alkali Soluble Thickener

A monomer mixture (300 grams) was prepared by charging ethyl acrylate(Aldrich), methacrylic acid (Aldrich), macromonomer M-1, 13 grams of a75% solution of Aerosol® OT surfactant (American Cyanamid, Stamford,Conn.), and 3 grams of distilled deionized water to a bottle, anddispersing the contents with vigorous shaking. The ethyl acrylate,methacrylic acid and macromonomer M-1 were added in amounts identifiedin Table C below. A catalyst feed mixture comprised of 0.53 grams ofsodium persulfate (Aldrich) and 52.47 grams of water was prepared inanother container. To a 2 liter resin flask that had been immersed in athermostated water bath and equipped with a 4-bladed stainless steelmechanical stirrer, Claisen connecting tube, water condenser, nitrogensparge and bubble trap, thermometer and monomer and catalyst additioninlets, 1.20 grams of the sodium salt of vinyl sulfonic acid and 658.5grams of water were charged. The monomer mixture was charged to a1-liter graduated monomer feed cylinder, and the catalyst solution wascharged to a 125 milliliter graduated catalyst feed cylinder. Undernitrogen purge, the reactor was heated to 70° C., whereupon 33milliliters of the monomer mixture and 3 milliliters of the catalystfeed mixture were charged to the reaction vessel. The reaction vesselwas subsequently heated to 80° C. After allowing the monomers to reactfor 20 minutes to form a seed product, the monomer and catalyst feedmixtures were conveyed to the reaction vessel by FMI pumps via 1/8"teflon tubing at a rate of 1.94 and 0.27 milliliters/minute,respectively, under continuous stirring at a reaction temperature heldbetween 76°-82° C. The reaction was allowed to proceed for another hour,after which the product was cooled and filtered with a 200 mesh nyloncloth. The coagulum was collected from the reaction vessel and filtercloth. Thickening ability of the resulting product was monitored byBrookfield viscosity at 6 rpm by diluting the latex to 0.25%, 0.50% and0.75% solids, and subsequently neutralizing the product to pH=9.0 with a95% solution of 2-amino-2-methyl-1-propanol (AMP-95, Angus ChemicalCompany). The results are given in Table C.

EXAMPLES 36-131 Preparation of Alkali Soluble Thickeners

In a manner similar to that described in Example 35, other alkalisoluble thickeners were prepared using the monomers identified in TablesC-J below in the amounts identified in Tables C-J. Table C illustratesthe influence of m-TMI-containing macromonomer concentration andethoxylation on thickening efficiency. Table D illustrates the influenceof mixing m-TMI-containing macromonomers of various ethoxylations onthickening efficiency. Table E illustrates the influence of unsaturationtype of urethane-containing macromonomers on thickening efficiency.Table F illustrates the influence of macromonomer ester structure andethoxylation on thickening efficiency. Table G illustrates the influenceof acid type and concentration on thickening efficiency. Table Hillustrates the influence of polymer glass transition temperature andwater solubility on thickening efficiency. Table I illustrates theinfluence of cross-linkable monomer concentration on thickeningefficiency. Table J illustrates the influence of mercaptan on thickeningefficiency. As used in Tables C-J below, the following abbreviationshave the indicated meanings: MM=Macromonomer; EA=Ethyl Acrylate;MAA=Methacrylic Acid; AA=Acrylic Acid; MA=Methyl Acrylate; t-BA=t-ButylAcrylate; n-BA=n-Butyl Acrylate; MMA=Methyl Methacrylate;2-EHP=2-Ethylhexyl Propionate Mercaptan; and 2-HEA=2-Hydroxy EthylAcrylate.

                                      TABLE C                                     __________________________________________________________________________                 Thickener Composition by                                                                   Brookfield Viscosity                                             Weight       (CPS) @ pH = 9.0                                                                           Thickener                              Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                            __________________________________________________________________________    35   M-1     10  50  40    90   380                                                                              1,000                                                                             P-1                                    36   M-2     5   55  40   270 11,400                                                                            103,600                                                                            P-2                                    37   M-2     10  50  40   120  3,100                                                                            60,000                                                                             P-3                                    38   M-2     10  50  40   105 10,400                                                                            130,000                                                                            P-3a                                   39   M-2     20  40  40    25  2,150                                                                            50,500                                                                             P-4                                    40   M-2     30  30  40    10   790                                                                             20,000                                                                             P-5                                    41   M-3     5   55  40   390  2,260                                                                            17,900                                                                             P-6                                    42   M-3     6.5 53.5                                                                              40   142  1,200                                                                            18,500                                                                             P-7                                    43   M-3     10  50  40   220  3,050                                                                            40,000                                                                             P-8                                    44   M-3     20  40  40    75  2,350                                                                            27,500                                                                             P-9                                    45   M-4     10  50  40   242  4,400                                                                            39,000                                                                             P-10                                   46   M-5     10  50  40    45  7,400                                                                            84,000                                                                             P-11                                   47   M-5     20  40  40    34  4,450                                                                            59,000                                                                             P-12                                   48   M-6     5   55  40   460 25,500                                                                            88,000                                                                             P-13                                   49   M-6     10  50  40   105 39,000                                                                            150,000                                                                            P-14                                   50   M-6     15  45  40   195 43,000                                                                            140,000                                                                            P-15                                   51   M-6     20  40  40   125 52,500                                                                            187,000                                                                            P-16                                   52   M-6     30  30  40   315 56,500                                                                            162,000                                                                            P-17                                   53   M-7     5   55  40   230  7,800                                                                            15,800                                                                             P-18                                   54   M-7     10  50  40   900 17,400                                                                            35,000                                                                             P-19                                   __________________________________________________________________________

                                      TABLE D                                     __________________________________________________________________________                 Thickener Composition by                                                                   Brookfield Viscosity                                             Weight       (CPS) @ pH = 9.0                                                                          Thickener                               Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              0.25%                                                                             0.50%                                                                             0.75%                                                                             Designation                             __________________________________________________________________________    55   M-3:M-6 10  50  40   225 24,000                                                                             85,000                                                                           P-20                                         1:1                                                                      56   M-2:M-6 10  50  40   135 21,200                                                                            134,000                                                                           P-21                                         1:1                                                                      __________________________________________________________________________

                                      TABLE E                                     __________________________________________________________________________                 Thickener Composition by                                                                   Brookfield Viscosity                                             Weight       (CPS) @ pH = 9.0                                                                           Thickener                              Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                            __________________________________________________________________________    57   M-8      5  55  40   250 14,800                                                                            124,000                                                                            P-22                                   58   M-8     10  50  40   93  11,200                                                                            125,400                                                                            P-23                                   59   M-8     20  40  40   45  6,140                                                                             84,500                                                                             P-24                                   60   M-9      5  55  40   275 6,200                                                                             57,000                                                                             P-25                                   61   M-9     10  50  40   250 10,100                                                                            80,000                                                                             P-26                                   62   M-9     20  40  40   90  7,800                                                                             90,000                                                                             P-27                                   63   M-9     30  30  40   45  5,200                                                                             69,000                                                                             P-28                                   __________________________________________________________________________

                                      TABLE F                                     __________________________________________________________________________                 Thickener Composition by                                                                   Brookfield Viscosity                                             Weight       (CPS) @ pH = 9.0                                                                           Thickener                              Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              0.25%                                                                              0.50%                                                                             0.75%                                                                             Designation                            __________________________________________________________________________    64   M-10    10  50  40   130    285                                                                                410                                                                            P-29                                   65   M-11    10  50  40   190  19,500                                                                            152,000                                                                           P-30                                   66   M-11    20  40  40   120  13,500                                                                            146,000                                                                           P-31                                   67   M-11    30  30  40    96   8,000                                                                             73,000                                                                           P-32                                   68   M-12     5  55  40   260   5,400                                                                             51,000                                                                           P-33                                   69   M-12    10  50  40   175   9,200                                                                             71,000                                                                           P-34                                   70   M-12    20  40  40   100   7,400                                                                             77,000                                                                           P-35                                   71   M-12    30  30  40    62   4,500                                                                             63,000                                                                           P-36                                   72   M-13     5  55  40   320  25,600                                                                             79,000                                                                           P-37                                   73   M-13    10  50  40    97  28,000                                                                            125,000                                                                           P-38                                   74   M-13    20  40  40   300  58,200                                                                            171,000                                                                           P-39                                   75   M-13    30  30  40   730  63,000                                                                            163,000                                                                           P-40                                   76   M-14    10  50  40   410  22,700                                                                            130,000                                                                           P-41                                   77   M-14    20  40  40   1225 44,500                                                                            168,000                                                                           P-42                                   78   M-14    30  30  40   1010 42,500                                                                            180,000                                                                           P-43                                   79   M-15     5  55  40    84   1,680                                                                             29,000                                                                           P-44                                   80   M-15    10  50  40   350  12,000                                                                             83,000                                                                           P-45                                   81   M-15    20  40  40   220  24,500                                                                            122,000                                                                           P-46                                   82   M-15    30  30  40   1050 33,000                                                                            133,000                                                                           P-47                                   83   M-16     5  55  40   450  17,720                                                                             45,300                                                                           P-48                                   84   M-16    10  50  40   1,345                                                                              27,000                                                                             98,000                                                                           P-49                                   85   M-16    20  40  40   3,450                                                                              65,800                                                                            158,000                                                                           P-50                                   86   M-16    30  30  40   11,600                                                                             81,000                                                                            157,000                                                                           P-51                                   87   M-17    10  50  40   410  12,000                                                                             60,000                                                                           P-52                                   88   M-17    20  40  40   255  10,600                                                                             46,300                                                                           P-53                                   89   M-17    30  30  40    38   2,525                                                                             13,500                                                                           P-54                                   90   M-18     5  55  40   100    810                                                                              3,500                                                                            P-55                                   91   M-18    10  50  40   110   1,420                                                                             5,940                                                                            P-56                                   92   M-18    20  40  40    30    870                                                                              2,425                                                                            P-57                                   __________________________________________________________________________

                                      TABLE G                                     __________________________________________________________________________                 Thickener Composition                                                                          Brookfield Viscosity                                         by Weight        (CPS) @ pH = 9.0                                                                           Thickener                          Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              % AA                                                                              0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                        __________________________________________________________________________    93   M-2     10  60  30   0   1520                                                                              12,200                                                                            102,000                                                                            P-58                               94   M-2     10  70  20   0    45  3,800                                                                            50,000                                                                             P-59                               95   M-2     10  80  10   0   <10   <10                                                                               <10                                                                              P-60                               96   M-2     10  60   0   30  <10    95                                                                              6,800                                                                             P-61                               97   M-6     20  60  20   0    15 13,500                                                                            43,500                                                                             P-62                               98   M-6      5  65  30   0   210 13,000                                                                            56,500                                                                             P-63                               99   M-6     10  60  30   0    77 24,000                                                                            88,000                                                                             P-64                               100  M-6     20  50  30   0    17  7,600                                                                            79,000                                                                             P-65                               101  M-6      5  45  50   0   130  7,060                                                                            28,000                                                                             P-66                               102  M-6     10  40  50   0    86 16,700                                                                            52,500                                                                             P-67                               103  M-6     20  30  50   0   130 28,000                                                                            122,000                                                                            P-68                               104   M-11   10  70   0   20  <10   213                                                                               7300                                                                             P-69                               105   M-17   10  50  20   20  710 16,500                                                                            66,000                                                                             P-70                               __________________________________________________________________________

                                      TABLE H                                     __________________________________________________________________________                 Thickener Composition                                                                           Brookfield Viscosity                                        by Weight         (CPS) @ pH = 9.0                                                                           Thickener                         Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              % Other                                                                            0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                       __________________________________________________________________________    106  M-2     10  40  40   10    90 5,760                                                                             82,000                                                                             P-71                                                        MMA                                                 107  M-2     10  30  40   20    15 1,125                                                                             55,000                                                                             P-72                                                        MMA                                                 108  M-2     10  20  40   30    10   207                                                                              6,000                                                                             P-73                                                        MMA                                                 109  M-2     10   0  40   50   <10  <10                                                                                <10                                                                              P-74                                                        MMA                                                 110  M-2     10  30  40   20    20   310                                                                              1,330                                                                             P-75                                                        styrene                                             111  M-2     10  40  40   10    95 7,540                                                                             75,500                                                                             P-76                                                        styrene                                             112  M-2     10  40  40   10   220 13,800                                                                            118,000                                                                            P-77                                                        n-BA                                                113  M-2     10  30  40   20   185 7,400                                                                             66,500                                                                             P-78                                                        n-BA                                                114  M-2     10  40  40   10   130 10,100                                                                            100,000                                                                            P-79                                                        t-BA                                                115  M-2     10  30  40   20   125 7,200                                                                             77,500                                                                             P-80                                                        t-BA                                                116  M-2     10  40  40   10   100 6,900                                                                             121,000                                                                            P-81                                                        MA                                                  117  M-2     10  30  40   20    73 5,000                                                                             90,000                                                                             P-82                                                        MA                                                  118  M-6     20  30  40   10    33 15,400                                                                            150,000                                                                            P-83                                                        MMA                                                 __________________________________________________________________________

                                      TABLE I                                     __________________________________________________________________________                 Thickener Composition                                                                            Brookfield Viscosity                                       by Weight          (CPS) @ pH = 9.0                                                                           Thickener                        Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              % 2-HEA                                                                             0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                      __________________________________________________________________________    119  M-2     10  47.7                                                                              40   2.3   97  9,060                                                                             127,000                                                                            P-84                             120  M-2     10  57.7                                                                              30   2.3   62  6,300                                                                             76,000                                                                             P-85                             121  M-2     20  37.5                                                                              40   2.5   27  6,200                                                                             116,600                                                                            P-86                             122  M-2     20  35  40   5     <10   260                                                                             18,600                                                                             P-87                             123  M-2     20  32.5                                                                              40   7.5   20    720                                                                             40,000                                                                             P-88                             124  M-2     20  30  40   10    10    520                                                                             29,500                                                                             P-89                             __________________________________________________________________________

                                      TABLE J                                     __________________________________________________________________________                 Thickener Composition                                                                            Brookfield Viscosity                                       by Weight          (CPS) @ pH = 9.0                                                                           Thickener                        Example                                                                            Macromonomer                                                                          % MM                                                                              % EA                                                                              % MAA                                                                              % 2-HEP*                                                                            0.25%                                                                             0.50%                                                                             0.75%                                                                              Designation                      __________________________________________________________________________    125  M-2     10  40  50   .05    165                                                                              22,800                                                                            142,000                                                                            P-90                             126  M-2     10  50  40   0.2    18  2,060                                                                            66,500                                                                             P-91                             127  M-2     10  50  40   0.3   <10   115                                                                              9,700                                                                             P-92                             128  M-2     10  50  40   0.5   <10    12                                                                               355                                                                              P-93                             129  M-2     10  50  40   1     <10   <10                                                                               <10                                                                              P-94                             130  M-6     10  50  40   .05    230                                                                              23,700                                                                            90,700                                                                             P-95                             131  M-6     10  50  40   .2     30  5,170                                                                            33,000                                                                             P-96                             __________________________________________________________________________     *% charged to reactor based on monomer.                                  

EXAMPLES 132-187 Co-Thickening with Surfactants

The addition of certain surfactants to an associative polymer solutionproduces a co-thickening effect. The results in Table L below show theco-thickening effect produced by the addition with thorough mixing ofcertain surfactants identified in Table K below in the amountsidentified in Table L to a 0.5% alkaline solution of an alkali solublethickener identified in Table L as measured with a Brookfield Viscometerat 6 rpm at pH=9.0.

                  TABLE K                                                         ______________________________________                                         ##STR11##                                                                                                     Moles of                                     Surfactant                                                                            R.sub.1     R.sub.2 /R.sub.3                                                                           Ethoxylation                                 ______________________________________                                        S-8     Nonylphenol Nonylphenol (R.sub.3)                                                                      20                                           S-9     Nonylphenol Nonylphenol (R.sub.3)                                                                      40                                           S-10    Nonylphenol Nonylphenol (R.sub.3)                                                                      80                                           S-11    Nonylphenol Hydrogen (R.sub.2)                                                                         25                                           S-12    Nonylphenol Hydrogen (R.sub.2)                                                                         40                                           S-13    Nonylphenol Octylphenol (R.sub.3)                                                                      20                                           S-14    Nonylphenol Octylphenol (R.sub.3)                                                                      40                                            S-15*  Nonylphenol Nonylphenol (R.sub.3)                                                                      40                                           S-16    Octylphenol Hydrogen (R.sub.2)                                                                         25                                           ______________________________________                                         *Sulfated derivative.                                                    

                  TABLE L                                                         ______________________________________                                                      Surfactant                                                      Exam- Surfac- Concentration                                                                             Thicken-                                                                             Brookfield Viscosity                         ple   tant    (wt. %)     er     (cps) @ pH = 9.0                             ______________________________________                                        132   S-8     0.0         P-3     3100                                              S-8     0.2         P-3    32700                                              S-8     0.4         P-3    45700                                              S-8     0.8         P-3    63300                                              S-8     1.0         P-3    65500                                              S-8     2.0         P-3    >100000                                      133   S-9     0.2         P-3    24200                                              S-9     0.4         P-3    18700                                              S-9     0.8         P-3     6600                                              S-9     1.0         P-3     4060                                                      2.0         P-3     1225                                        134   S-10    0.2         P-3    20600                                              S-10    0.4         P-3    17300                                              S-10    0.8         P-3     8500                                              S-10    1.0         P-3     6300                                              S-10    2.0         P-3     1850                                        135   S-11    0.2         P-3    12000                                              S-11    0.4         P-3     3160                                              S-11    0.8         P-3     700                                               S-11    1.0         P-3     485                                               S-11    2.0         P-3     480                                         136   S-12    0.2         P-3     9200                                              S-12    0.4         P-3     4500                                              S-12    0.8         P-3     1000                                              S-12    1.0         P-3     875                                               S-12    2.0         P-3     565                                         137   S-13    0.2         P-3    34300                                              S-13    0.4         P-3    26700                                              S-13    0.8         P-3    11500                                              S-13    1.0         P-3     8600                                              S-13    2.0         P-3     2450                                        138   S-14    0.2         P-3    22200                                              S-14    0.4         P-3    17200                                              S-14    0.8         P-3     6900                                              S-14    1.0         P-3     4500                                              S-14    2.0         P-3     1500                                        139   S-15    0.2         P-3    10500                                              S-15    0.4         P-3     4940                                              S-15    0.8         P-3     2160                                              S-15    1.0         P-3     1450                                              S-15    2.0         P-3     355                                         140   S-16    0.2         P-3    14300                                              S-16    0.4         P-3     4080                                              S-16    0.8         P-3     1075                                              S-16    1.0         P-3     735                                               S-16    2.0         P-3     485                                         141   S-8     0.0         P-2    11400                                              S-8     0.2         P-2    23500                                              S-8     0.4         P-2    34000                                              S-8     0.8         P-2    64000                                              S-8     1.0         P-2    71000                                              S-8     2.0         P-2    93000                                        142   S-9     0.2         P-2    11000                                              S-9     0.4         P-2     4000                                              S-9     0.8         P-2     2000                                              S-9     1.0         P-2     1400                                              S-9     2.0         P-2     850                                         143   S-10    0.2         P-2    10500                                              S-10    0.4         P-2     5000                                              S-10    0.8         P-2     2000                                              S-10    1.0         P-2     1600                                              S-10    2.0         P-2     950                                         144   S-11    0.2         P-2     2700                                              S-11    0.4         P-2     1000                                              S-11    0.8         P-2     800                                               S-11    1.0         P-2     660                                               S-11    2.0         P-2     620                                         145   S-12    0.2         P-2     2800                                              S-12    0.4         P-2     1000                                              S-12    0.8         P-2     850                                               S-12    1.0         P-2     660                                               S-12    2.0         P-2     650                                         146   S-8     0.0         P-4     2150                                              S-8     0.2         P-4    19000                                              S-8     0.4         P-4    31000                                              S-8     0.8         P-4    55000                                              S-8     1.0         P-4    61000                                              S-8     2.0         P-4    85000                                        147   S-9     0.2         P-4    19500                                              S-9     0.4         P-4    21500                                              S-9     0.8         P-4    11500                                              S-9     1.0         P-4     7400                                              S-9     2.0         P-4     2250                                        148   S-10    0.2         P-4    12600                                              S-10    0.4         P-4    17400                                              S-10    0.8         P-4    12600                                              S-10    1.0         P-4     6600                                              S-10    2.0         P-4     2600                                        149   S-11    0.2         P-4    17400                                              S-11    0.4         P-4     7800                                              S-11    0.8         P-4     1650                                              S-11    1.0         P-4     860                                               S-11    2.0         P-4     560                                         150   S-12    0.2         P-4    14600                                              S-12    0.4         P-4     7800                                              S-12    0.8         P-4     1500                                              S-12    1.0         P-4     960                                               S-12    2.0         P-4     450                                         151   S-8     0.0         P-5     790                                               S-8     0.2         P-5     4600                                              S-8     0.4         P-5    19600                                              S-8     0.8         P-5    42000                                              S-8     1.0         P-5    50000                                              S-8     2.0         P-5    90000                                        152   S-9     0.2         P-5     5800                                              S-9     0.4         P-5    13200                                              S-9     0.8         P-5     9200                                              S-9     1.0         P-5     5200                                              S-9     2.0         P-5     1600                                        153   S-10    0.2         P-5     4050                                              S-10    0.4         P-5    10400                                              S-10    0.8         P-5     9400                                              S-10    1.0         P-5     5000                                              S-10    2.0         P-5     1600                                        154   S-11    0.2         P-5    10600                                              S-11    0.4         P-5     4200                                              S-11    0.8         P-5     1400                                              S-11    1.0         P-5     970                                               S-11    2.0         P-5     410                                         155   S-12    0.2         P-5     6000                                              S-12    0.4         P-5     4200                                              S-12    0.8         P-5     1150                                              S-12    1.0         P-5     600                                               S-12    2.0         P-5     340                                         156   S-8     0           P-7     1200                                              S-8     0.2         P-7     9000                                              S-8     0.4         P-7    21000                                              S-8     0.8         P-7    37000                                              S-8     1.0         P-7    49000                                              S-8     2.0         P-7    78000                                        157   S-9     0.2         P-7     1600                                              S-9     0.4         P-7     1350                                              S-9     0.8         P-7     900                                               S-9     1.0         P-7     762                                               S-9     2.0         P-7      565                                        158   S-10    0.2         P-7     1100                                              S-10    0.4         P-7     1150                                              S-10    0.8         P-7     900                                               S-10    1.0         P-7     823                                               S-10    2.0         P-7     650                                         159   S-11    0.2         P-7     1175                                              S-11    0.4         P-7     685                                               S-11    0.8         P-7     503                                               S-11    1.0         P-7     495                                               S-11    2.0         P-7     502                                         160   S-12    0.2         P-7     950                                               S-12    0.4         P-7     675                                               S-12    0.8         P-7     525                                               S-12    1.0         P-7     500                                               S-12    2.0         P-7     480                                         161   S-8     0.0         P-13   25500                                              S-8     0.2         P-13   31500                                              S-8     0.4         P-13   46500                                              S-8     0.8         P-13   60000                                              S-8     1.0         P-13   60000                                              S-8     2.0         P-13   62500                                        162   S-9     0.2         P-13    8640                                              S-9     0.4         P-13    2940                                              S-9     0.8         P-13    1200                                              S-9     1.0         P-13    1000                                              S-9     2.0         P-13    750                                         163   S-10    0.2         P-13   10100                                              S-10    0.4         P-13    4200                                              S-10    0.8         P-13    1450                                              S-10    1.0         P-13    1300                                              S-10    2.0         P-13    900                                         164   S-12    0.2         P-13    2540                                              S-12    0.4         P-13    1125                                              S-12    0.8         P-13    750                                               S-12    1.0         P-13    670                                               S-12    2.0         P-13    610                                         165   S-8     0.0         P-14   39000                                              S-8     0.2         P-14   61000                                              S-8     0.4         P-14   73500                                              S-8     0.8         P-14   87000                                              S-8     1.0         P-14   93500                                              S-8     2.0         P-14   122000                                       166   S-9     0.2         P-14   41000                                              S-9     0.4         P-14   13700                                              S-9     0.8         P-14    6200                                              S-9     1.0         P-14    3500                                              S-9     2.0         P-14    1200                                        167   S-10    0.2         P-14   38200                                              S-10    0.4         P-14   20500                                              S-10    0.8         P-14    7300                                              S-10    1.0         P-14    5400                                              S-10    2.0         P-14    1950                                        168   S-12    0.2         P-14   13000                                              S-12    0.4         P-14    4300                                              S-12    0.8         P-14    975                                               S-12    1.0         P-14    950                                               S-12    2.0         P-14    660                                         169   S-8     0.0         P-16   52500                                              S-8     0.2         P-16   95000                                              S-8     0.4         P-16   92000                                              S-8     0.8         P-16   122000                                             S-8     1.0         P-16   125000                                             S-8     2.0         P-16   138000                                       170   PS-9    0.2         P-16   73500                                              PS-9    0.4         P-16   53000                                              PS-9    0.8         P-16   25000                                              PS-9    1.0         P-16   21000                                              PS-9    2.0         P-16    5400                                        171   S-10    0.2         P-16   52800                                              S-10    0.4         P-16   34500                                              S-10    0.8         P-16     5400                                             S-10    1.0         P-16    2925                                              S-10    2.0         P-16    775                                         172   S-13    0.2         P-16   45800                                              S-13    0.4         P-16   54000                                              S-13    0.8         P-16   50800                                              S-13    1.0         P-16   54500                                              S-13    2.0         P-16   63000                                        173   S-14    0.2         P-16   22700                                              S-14    0.4         P-16    2480                                              S-14    0.8         P-16    710                                               S-14    1.0         P-16    532                                               S-14    2.0         P-16    415                                         174   S-8     0.0         P-29    285                                               S-8     0.2         P-29    285                                               S-8     0.4         P-29    360                                               S-8     0.8         P-29    477                                               S-8     1.0         P-29    505                                               S-8     2.0         P-29    837                                         175   S-9     0.2         P-29    282                                               S-9     0.4         P-29    285                                               S-9     0.8         P-29    284                                               S-9     1.0         P-29    298                                               S-9     2.0         P-29    322                                         176   S-10    0.2         P-29    272                                               S-10    0.4         P-29    278                                               S-10    0.8         P-29    285                                               S-10    1.0         P-29    297                                               S-10    2.0         P-29    315                                         177   S-12    0.2         P-29    267                                               S-12    0.4         P-29    279                                               S-12    0.8         P-29    298                                               S-12    1.0         P-29    311                                               S-12    2.0         P-29    320                                         178   S-8     0.0         P-30   19500                                              S-8     0.2         P-30   79000                                              S-8     0.4         P-30   71200                                              S-8     0.8         P-30   81000                                              S-8     1.0         P-30   89500                                              S-8     2.0         P-30   175000                                       179   S-9     0.2         P-30   52000                                              S-9     0.4         P-30   35500                                              S-9     0.8         P-30   16500                                              S-9     1.0         P-30   15600                                              S-9     2.0         P-30    5620                                        180   S-10    0.2         P-30   47200                                              S-10    0.4         P-30   26300                                              S-10    0.8         P-30   20300                                              S-10    1.0         P-30   13400                                              S-10    2.0         P-30    4700                                        181   S-12    0.2         P-30   23000                                              S-12    0.4         P-30    6840                                              S-12    0.8         P-30    3125                                              S-12    1.0         P-30    1750                                              S-12    2.0         P-30    1225                                        182   S-8     0.0         P-46   24500                                              S-8     0.2         P-46   79000                                              S-8     0.4         P-46   75000                                              S-8     0.8         P-46   86000                                              S-8     1.0         P-46   95000                                              S-8     2.0         P-46   150000                                       183   S-9     0.2         P-46   40500                                              S-9     0.4         P-46   31000                                              S-9     0.8         P-46   15300                                              S-9     1.0         P-46    9400                                              S-9     2.0         P-46    2300                                        184   S-11    0.2         P-46   20000                                              S-11    0.4         P-46    7300                                              S-11    0.8         P-46    1350                                              S-11    1.0         P-46    900                                               S-11    2.0         P-46    380                                         185   S-13    0.2         P-46   63500                                              S-13    0.4         P-46   42000                                              S-13    0.8         P-46   23000                                              S-13    1.0         P-46   16000                                              S-13    2.0         P-46    4850                                        186   S-14    0.2         P-46   36000                                              S-14    0.4         P-46   25000                                              S-14    0.8         P-46   11000                                              S-14    1.0         P-46    9300                                              S-14    2.0         P-46    1900                                        187   S-16    0.2         P-46   19000                                              S-16    0.4         P-46    9300                                              S-16    0.8         P-46    1250                                              S-16    1.0         P-46    750                                               S-16    2.0         P-46    290                                         ______________________________________                                    

EXAMPLES 188-232 Co-Thickening with Surfactants

The degree of ethoxylation of a surfactant added to an associativepolymer solution influences the co-thickening effect. The results inTable N below show the co-thickening effect produced by the additionwith thorough mixing of certain surfactants identified in Table M belowin the amounts identified in Table N to a 0.3% (Examples 172-189), 0.5%(Examples 190-215) or 0.75% (Example 216) alkaline solution of an alkalisoluble thickener identified in Table N as measured with a BrookfieldViscometer at 6 rpm at pH=9.0.

                  TABLE M                                                         ______________________________________                                         ##STR12##                                                                                                     Moles of                                     Surfactant                                                                            R.sub.1     R.sub.2 /R.sub.3                                                                           Ethoxylation                                 ______________________________________                                        S-17    Nonylphenol Hydrogen (R.sub.2)                                                                         4                                            S-18    Nonylphenol Hydrogen (R.sub.2)                                                                         6                                            S-19    Nonylphenol Hydrogen (R.sub.2)                                                                         7                                            S-20    Nonylphenol Hydrogen (R.sub.2)                                                                         8                                            S-21    Nonylphenol Hydrogen (R.sub.2)                                                                         9                                            S-22    Nonylphenol Hydrogen (R.sub.2)                                                                         10                                           S-23    Nonylphenol Hydrogen (R.sub.2)                                                                         15                                           S-24    Nonylphenol Hydrogen (R.sub.2)                                                                         25                                           S-25    Nonylphenol Hydrogen (R.sub.2)                                                                         40                                           S-26    Octylphenol Hydrogen (R.sub.2)                                                                         1                                            S-27    Octylphenol Hydrogen (R.sub.2)                                                                         3                                            S-28    Octylphenol Hydrogen (R.sub.2)                                                                         5                                            S-29    Octylphenol Hydrogen (R.sub.2)                                                                         7                                            S-30    Octylphenol Hydrogen (R.sub.2)                                                                         9                                            S-31    Octylphenol Hydrogen (R.sub.2)                                                                         12                                           S-32    Octylphenol Hydrogen (R.sub.2)                                                                         16                                           S-33    C11-C15     Hydrogen (R.sub.2)                                                                         5                                                    Secondary                                                                     Alcohol                                                               S-34    C11-C15     Hydrogen (R.sub.2 )                                                                        9                                                    Secondary                                                                     Alcohol                                                               ______________________________________                                    

                  TABLE N                                                         ______________________________________                                                                             Brookfield                                                 Surfactant         Viscosity                                Exam-             Concentration                                                                             Thicken-                                                                             (cps) @                                  ple   Surfactant  (wt. %)     er     pH = 9.0                                 ______________________________________                                        188   S-17        0.8         P-1     890                                     189   S-18        0.8         P-1     1340                                    190   S-19        0.8         P-1     630                                     191   S-20        0.8         P-1     205                                     192   S-21        0.8         P-1     143                                     193   S-22        0.8         P-1     113                                     194   S-23        0.8         P-1      85                                     195   S-24        0.8         P-1      57                                     196   S-25        0.8         P-1      68                                     197   S-17        0.8         P-3    17800                                    198   S-18        0.8         P-3    35800                                    199   S-19        0.8         P-3    21300                                    200   S-20        0.8         P-3     820                                     201   S-21        0.8         P-3     230                                     202   S-22        0.8         P-3     147                                     203   S-23        0.8         P-3     118                                     204   S-24        0.8         P-3      82                                     205   S-25        0.8         P-3      77                                     206   S-17        0.8         P-42   57000                                    207   S-18        0.8         P-42   134000                                   208   S-19        0.8         P-42   112000                                   209   S-21        0.8         P-42    2450                                    210   S-22        0.8         P-42    800                                     211   S-23        0.8         P-42    3250                                    212   S-26        0.8         P-42   43000                                    213   S-27        0.8         P-42   37000                                    214   S-28        0.8         P-42   71000                                    215   S-29        0.8         P-42    5800                                    216   S-30        0.8         P-42    375                                     217   S-31        0.8         P-42    650                                     218   S-32        0.8         P-42    2400                                    219   S-17        0.8         P-46   68000                                    220   S-18        0.8         P-46   13000                                    221   S-19        0.8         P-46   88000                                    222   S-21        0.8         P-46    2900                                    223   S-22        0.8         P-46    1400                                    224   S-23        0.8         P-46    2400                                    225   S-26        0.8         P-46   25000                                    226   5-27        0.8         P-46   38500                                    227   S-28        0.8         P-46   77000                                    228   S-29        0.8         P-46    7200                                    229   S-30        0.8         P-46    550                                     230   S-31        0.8         P-46    690                                     231   S-32        0.8         P-46    1775                                    232   Aerosol ® OT                                                                          0.0         P-4    50500                                          Aerosol ® OT                                                                          0.1         P-4    93500                                          Aerosol ® OT                                                                          0.2         P-4    42000                                          Aerosol ® OT                                                                          0.4         P-4    11200                                          Aerosol ® OT                                                                          0.8         P-4     3700                                          Aerosol ® OT                                                                          1.0         P-4     7200                                          Aerosol ® OT                                                                          2.0         P-4    10600                                    ______________________________________                                    

EXAMPLES 233-245 Co-Thickening with Solvents and Non-Solvents

Solvents and non-solvents added to an associative polymer solutioninfluences the co-thickening effect. The results in Table P below showthe co-thickening effect produced by the addition with thorough mixingof certain solvents and non-solvents identified in Table O below in theamounts identified in Table P to a 0.75% alkaline solution of an alkalisoluble thickener identified in Table P as measured with a BrookfieldViscometer at 6 rpm at pH=9.0.

                  TABLE O                                                         ______________________________________                                        Solvent                                                                       Designation       Solvent                                                     ______________________________________                                        O-1               mineral spirits                                             O-2               butanol                                                     O-3               Isobutanol                                                  O-4               Isopropanol                                                 O-5               2-Ethylhexanol                                              O-6               Butyl Carbitol                                              O-7               Butyl DiPropasol                                            O-8               Butyl Propasol                                              O-9               Propyl DiPropasol                                            O-10             Propyl Propasol                                              O-11             Methyl DiPropasol                                            O-12             Methyl Propasol                                             ______________________________________                                    

                                      TABLE P                                     __________________________________________________________________________                    Solvent Solvent O-1                                                                           Brookfield                                                    Concentration                                                                         Concentration                                                                         Viscosity                                     Example                                                                            Thickener                                                                           Solvent                                                                            (wt. %) (wt. %) (cps) @ pH = 9.0                              __________________________________________________________________________    233  P-3   O-6   5      0       29200                                              P-3   O-6  10      0        865                                               P-3   O-6  20      0        625                                               P-3   O-6  40      0        720                                               P-3   O-6   5      5       15400                                              P-3   O-6  10      5        1125                                              P-3   O-6  20      5        735                                               P-3   O-6  40      5        780                                               P-3   O-6   5      10      56500                                              P-3   O-6  10      10       1050                                              P-3   O-6  20      10       835                                               P-3   O-6  40      10       832                                               P-3   O-6   5      20      41500                                              P-3   O-6  10      20       1625                                         234  P-3   O-7   0      0       76000                                              P-3   O-7   5      0        2150                                              P-3   O-7  10      0        3700                                              P-3   O-7  20      0        2000                                              P-3   O-7   0      5       89000                                              P-3   O-7   5      5       88000                                              P-3   O-7  10      5       50000                                              P-3   O-7  20      5       46500                                              P-3   O-7   0      10      102400                                             P-3   O-7   5      10      122000                                             P-3   O-7  10      10      72000                                              P-3   O-7   0      20      113000                                             P-3   O-7   5      20      158000                                             P-3   O-7  10      20      138000                                        235  P-3   O-8   5      0        1925                                              P-3   O-8  10      0        1150                                              P-3   O-8  20      0        2000                                              P-3   O-8  40      0        6200                                         236  P-3   O-9   5      0       36000                                              P-3   O-9  10      0        1200                                              P-3   O-9  20      0        440                                               P-3   O-9  40      0        1375                                         237  P-3    O-10                                                                               5      0        1375                                              P-3    O-10                                                                              10      0       45500                                              P-3    O-10                                                                              20      0        625                                               P-3    O-10                                                                              40      0        510                                          238  P-3    O-11                                                                               5      0       36000                                              P-3    O-11                                                                              10      0       20500                                              P-3    O-11                                                                              20      0        4200                                              P-3    O-11                                                                              40      0        550                                          239  P-3    O-12                                                                               0      0       76000                                              P-3    O-12                                                                               5      0       45000                                              P-3    O-12                                                                              10      0       24500                                              P-3    O-12                                                                              20      0        5800                                              P-3    O-12                                                                              40      0        675                                               P-3    O-12                                                                               5      5       51500                                              P-3    O-12                                                                              10      5       28500                                              P-3    O-12                                                                              20      5        7100                                              P-3    O-12                                                                              40      5        810                                               P-3    O-12                                                                               5      10      61200                                              P-3    O-12                                                                              10      10      33500                                              P-3    O-12                                                                              20      10       6400                                              P-3    O-12                                                                              40      10       950                                               P-3    O-12                                                                               5      20      86800                                              P-3    O-12                                                                              10      20      40500                                              P-3    O-12                                                                              20      20       7100                                              P-3    O-12                                                                              40      20       1350                                         240  P-14  O-7   0      0       150000                                             P-14  O-7   5      0        1350                                              P-14  O-7  10      0        4500                                              P-14  O-7  20      0        7000                                              P-14  O-7   0      5       140000                                             P-14  O-7   5      5       120000                                             P-14  O-7  10      5       78000                                              P-14  O-7   0      5       140000                                             P-14  O-7   5      10      158000                                             P-14  O-7  10      10      124000                                             P-14  O-7   0      20      136000                                             P-14  O-7   5      20      152000                                             P-14  O-7  10      20      142000                                        241  P-3a  O-2   0      0       132600                                             P-3a  O-2   5      0       17300                                              P-3a  O-2  10      0        850                                               P-3a  O-2  20      0        1425                                              P-3a  O-2  40      0        4750                                              P-3a  O-2   0      5       140000                                             P-3a  O-2   5      5       67000                                              P-3a  O-2  10      5        2500                                              P-3a  O-2  20      5        3000                                              P-3a  O-2   0      10      134000                                             P-3a  O-2   5      10      33000                                              P-3a  O-2  10      10       4000                                              P-3a  O-2  20      10       4900                                              P-3a  O-2   0      20      144000                                             P-3a  O-2   5      20      49000                                              P-3a  O-2  10      20       8000                                         242  P-3a  O-3   5      0       28500                                              P-3a  O-3  10      0        880                                               P-3a  O-3  20      0        1425                                              P-3a  O-3  40      0        4600                                              P-3a  O-3   5      5       80000                                              P-3a  O-3  10      5        2950                                              P-3a  O-3  20      5        3200                                              P-3a  O-3  40      5        6200                                              P-3a  O-3   5      10      78000                                              P-3a  O-3  10      10       5200                                              P-3a  O-3  20      10       6400                                              P-3a  O-3   5      20      136000                                             P-3a  O-3  10      20      20500                                         243  P-3a  O-4   5      0       94000                                              P-3a  O-4  10      0       29000                                              P-3a  O-4  20      0        1050                                              P-3a  O-4  40      0        850                                               P-3a  O-4   5      5       107400                                             P-3a  O-4  10      5       39000                                              P-3a  O-4  20      5        1225                                              P-3a  O-4  40      5        900                                               P-3a  O-4   5      10      134000                                             P-3a  O-4  10      10      41000                                              P-3a  O-4  20      10       1350                                              P-3a  O-4  40      10       1050                                              P-3a  O-4   5      20      164000                                             P-3a  O-4  10      20      33000                                              P-3a  O-4  20      20       1825                                              P-3a  O-4  40      20       1350                                         244  P-3a  O-5   5      0       93500                                              P-3a  O-5  10      0       136000                                             P-3a  O-5  20      0       178000                                        245  P-3a  O-7   5      0        2700                                              P-3a  O-7  10      0        6100                                              P-3a  O-7  20      0       11900                                         __________________________________________________________________________

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

We claim:
 1. A process of thickening an aqueous composition comprisingadding to the composition a polymer and at least partially neutralizingsaid polymer, wherein said polymer comprises the reaction product of:(A)about 1-99.9 weight percent of one or more alpha, beta-monoethylenicallyunsaturated carboxylic acids; (B) about 0-98.9 weight percent of one ormore monoethylenically unsaturated monomers; (C) about 0.1-99 weightpercent of one or more monoethylenically unsaturated macromonomers; and(D) about 0-20 weight percent or greater of one or morepolyethylenically unsaturated monomers.
 2. The process of claim 1wherein the composition is thickened further by the addition of aneffective amount of surfactant, solvent or non-solvent.
 3. A process forthickening an aqueous composition which comprises:(1) adding a polymerto the aqueous composition which polymer is prepared by polymerizingmonomers comprising:(a) about 1-99.9 weight percent of one or morealpha, beta-monoethylenically unsaturated carboxylic acids; (b) about0-98.9 weight percent of one or more monoethylenically unsaturatedmonomers; (c) about 0.1-99 weight percent of one or moremonoethylenically unsaturated macromonomers; and (d) about 0-20 weightpercent or greater of one or more polyethylenically unsaturatedmonomers; and (2) dissolving the polymer in the aqueous composition. 4.The process of claim 3 wherein the aqueous composition is a latex paintcomposition wherein the polymer is dissolved in said paint compositionin an amount of about 0.05 to about 5% by weight of the paintcomposition.
 5. The process of claim 1 wherein said monoethylenicallyunsaturated macromonomer is represented by the formula: ##STR13##wherein: R¹ is a monovalent residue of a substituted or unsubstitutedcomplex hydrophobe compound;each R² is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue; R³ is asubstituted or unsubstituted divalent hydrocarbon residue; R⁴, R⁵ and R⁶are the same or different and are hydrogen or a substituted orunsubstituted monovalent hydrocarbon residue; and z is a value of 0 orgreater, in which said substituted or unsubstituted complex hydrophobecompound is represented by the formula selected from: ##STR14## whereinR_(l) and R₂ are the same or different and are hydrogen or a substitutedor unsubstituted monovalent hydrocarbon residue, R₃ is a substituted orunsubstituted divalent or trivalent hydrocarbon residue, each R₄ is thesame or different and is a substituted or unsubstituted divalenthydrocarbon residue, each R₅ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue, R₆ ishydrogen, a substituted or unsubstituted monovalent hydrocarbon residueor an ionic substituent, a and b are the same or different and are avalue of 0 or 1, and x and y are the same or different and are a valueof 0 or greater; provided at least two of R₁, R₂, R₃, R₄, R₅ and R₆ area hydrocarbon residue having greater than 2 carbon atoms in the case ofR₁, R₂ and R₆ or having greater than 2 pendant carbon atoms in the caseof R₃, R₄ and R₅ ; and ##STR15## wherein R₇ and R₈ are the same ordifferent and are hydrogen or a substituted or unsubstituted monovalenthydrocarbon residue, R₉ and R₁₂ are the same or different and are asubstituted or unsubstituted divalent or trivalent hydrocarbon residue,each R₁₀ is the same or different and is a substituted or unsubstituteddivalent hydrocarbon residue, each R₁₃ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue, R₁₁ and R₁₄are the same or different and are hydrogen, a substituted orunsubstituted monovalent hydrocarbon residue or an ionic substituent,R₁₅ is a substituted or unsubstituted divalent hydrocarbon residue, dand e are the same or different and are a value of 0 or 1, and f and gare the same or different and are a value of 0 or greater; provided atleast two of R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are ahydrocarbon residue having greater than 2 carbon atoms in the case ofR₇, R₈, R₁₁ an R₁₄ or having greater than 2 pendant carbon atoms in thecase of R₉, R₁₀, R₁₂, R₁₃ and R₁₅.
 6. The process of claim 5 wherein R₁,R₂, R₇ and R₈ are selected from substituted or unsubstituted alkyl,aryl, alkylaryl, arylalkyl, cycloalkyl or mixtures thereof.
 7. Theprocess of claim 5 wherein R₁, R₂, R₇ and R₈ are selected fromdodecylphenyl, nonylphenyl, octylphenyl or mixtures thereof.
 8. Theprocess of claim 5 wherein each R₄, R₅, R₁₀ and R₁₃ is selected from--CH₂ CH₂ --, --CH₂ CH(CH₃)-- or mixtures thereof.
 9. The process ofclaim 5 wherein the values of x, y, f and g are from 0 to about 200 orgreater.
 10. The process of claim 5 in which said monoethylenicallyunsaturated macromonomer is represented by the formula selected from:##STR16## wherein R¹, R², R⁴, and z are as defined in claim 5, each R₁₉is the same or different and is a substituted or unsubstituted divalenthydrocarbon residue and j is a value of 0 or greater.
 11. The process ofclaim 5 in which said component (A) is methacrylic acid, component (B)is ethyl acrylate, and component (C) contains styryl, acrylic, allylic,methacrylic or crotonic unsaturation.
 12. The process of claim 3 whereinsaid monoethylenically unsaturated macromonomer is represented by theformula: ##STR17## wherein: R¹ is a monovalent residue of a substitutedor unsubstituted complex hydrophobe compound;each R² is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue; R³ is a substituted or unsubstituted divalent hydrocarbonresidue; R⁴, R⁵ and R⁶ are the same or different and are hydrogen or asubstituted or unsubstituted monovalent hydrocarbon residue; and z is svalue of 0 or greater; in which said substituted or unsubstitutedcomplex hydrophobe compound is represented by the formula selected from:##STR18## wherein R₁ and R₂ are the same or different and are hydrogenor a substituted or unsubstituted monovalent hydrocarbon residue, R₃ isa substituted or unsubstituted divalent or trivalent hydrocarbonresidue, each R₄ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, each R₅ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, R₆ is hydrogen, a substituted or unsubstituted monovalenthydrocarbon residue or an ionic substituent, a and b are the same ordifferent and are a value of 0 or 1, and x and y are the same ordifferent and are a value of 0 or greater; provided at least two of R₁,R₂, R₃, R₄, R₅ and R₆ are a hydrocarbon residue having greater than 2carbon atoms in the case of R₁, R₂ and R₆ or having greater than 2pendant carbon atoms in the case of R₃, R₄ and R₅ ; and ##STR19##wherein R₇ and R₈ are the same or different and are hydrogen or asubstituted or unsubstituted monovalent hydrocarbon residue, R₉ and R₁₂are the same or different and are a substituted or unsubstituteddivalent or trivalent hydrocarbon residue, each R₁₀ is the same ordifferent and is a substituted or unsubstituted divalent hydrocarbonresidue, each R₁₃ is the same or different and is a substituted orunsubstituted divalent hydrocarbon residue, R₁₁ and R₁₄ are the same ordifferent and are hydrogen, a substituted or unsubstituted monovalenthydrocarbon residue or an ionic substituent, R₁₅ is a substituted orunsubstituted divalent hydrocarbon residue, d and e are the same ordifferent and are a value of 0 or 1, and f and g are the same ordifferent and are a value of 0 or greater; provided at least two of R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ are a hydrocarbon residue havinggreater than 2 carbon atoms in the case of R₇, R₈, R₁₁ an R₁₄ or havinggreater than 2 pendant carbon atoms in the case of R₉, R₁₀, R₁₂, R₁₃ andR₁₅.
 13. The process of claim 12 wherein R₁, R₂, R₇ and R₈ are selectedfrom substituted or unsubstituted alkyl, aryl, alkylaryl, arylalkyl,cycloalkyl or mixtures thereof.
 14. The process of claim 12 wherein R₁,R₂, R₇ and R₈ are selected from dodecylphenyl, nonylphenyl, octylphenylor mixtures thereof.
 15. The process of claim 12 wherein each R₄, R₅,R₁₀ and R₁₃ is selected from --CH₂ CH₂ --, --CH₂ CH(CH₃)-- or mixturesthereof.
 16. The process of claim 12 wherein the values of x, y, f and gare from 0 to about 200 or greater.
 17. The process of claim 12 in whichsaid monoethylenically unsaturated macromonomer is represented by theformula selected from: ##STR20## wherein R¹, R², R⁴, and z are asdefined in claim 12, each R₁₉ is the same or different and is asubstituted or unsubstituted divalent hydrocarbon residue and j is avalue of 0 or greater.
 18. The process of claim 12 in which saidcomponent (A) is methacrylic acid, component (B) is ethyl acrylate, andcomponent (C) contains styryl, acrylic, allylic, methacrylic or crotonicunsaturation.